TW201333117A - Coating composition, forous membrane, light scattering membrane, and organic electroluminescent element - Google Patents

Abstract

The objection of invention is to provide a coating composition capable of easily forming by coating or likes, and a porous membrane and light scattering membrane which are excellent in a heat resistance, a surface smoothness and flexibility, and have a high refractive index, a high light scattering property and a high light transmittance, and further an organic electroluminescent element containing the light scattering membrane. It has been found that a cured product obtained by curing a composition containing a polysilane, a metal oxide and a solvent, has a void inside it. The cured product having the void inside it, has a light scattering property, thus, is applicable to a light scattering membrane.

Description

塗佈用組成物、多孔質膜、光散射膜及有機電場發光元件 Coating composition, porous film, light scattering film, and organic electroluminescent element

本發明係關於塗佈用組成物、利用塗佈該塗佈用組成物而獲得之多孔質膜、光散射膜、及具有該光散射膜的有機電場發光元件。 The present invention relates to a coating composition, a porous film obtained by applying the coating composition, a light-scattering film, and an organic electroluminescence device having the light-scattering film.

有機電場發光元件(以下稱「有機EL」)係由含有玻璃基板上的陽極、陰極、以及在二電極間所形成發光層構成。藉由對二電極的通電而在發光層產生的光，會通過陽極(例如ITO等透明電極)與玻璃基板而被取出於外部。但是，已知在ITO與玻璃基板、及玻璃基板與大氣的界面處，會因折射率差而產生反射，因而大部分發光並無法被取出於外部，被取出於外部的光係發光之約20%左右。 The organic electroluminescent device (hereinafter referred to as "organic EL") is composed of an anode including a glass substrate, a cathode, and a light-emitting layer formed between the electrodes. Light generated in the light-emitting layer by energization of the two electrodes is taken out to the outside through an anode (for example, a transparent electrode such as ITO) and a glass substrate. However, it is known that at the interface between the ITO and the glass substrate and between the glass substrate and the atmosphere, reflection occurs due to the difference in refractive index, so that most of the light is not taken out and the light emitted from the outside is about 20 %about.

為改善有機電場發光元件的光取出效率，便有報告嘗試在屬於陽極的ITO等透明電極與玻璃基板之間設置散射層。例如專利文獻1有報告指出：使用由玻璃料(粉體)一起與樹脂形成混練油墨，塗佈於玻璃基板上，依高溫施行煅燒．加熱，而將玻璃料予以熔融且使樹脂燒磬，便使氣泡內含於玻璃介質內的散射層。 In order to improve the light extraction efficiency of the organic electroluminescent element, it has been reported that a scattering layer is provided between a transparent electrode such as ITO belonging to the anode and the glass substrate. For example, Patent Document 1 reports that: using a glass frit (powder) together with a resin to form a kneading ink, coated on a glass substrate, and calcined at a high temperature. Heating, while melting the glass frit and burning the resin, the bubbles are contained in the scattering layer in the glass medium.

專利文獻2有報告指出：將含有以氧化鋅為散射粒子的丙烯酸系樹脂溶液，利用旋塗塗佈而獲得之散射層。再者，專利文獻3所報告的主旨：將四乙氧基矽烷之水解物的溶膠-凝膠溶液、與粒徑 80nm二氧化矽溶膠溶液的混合物，利用旋塗施行塗佈，經依300℃加熱而獲得之硬化皮膜，使用為散射層。 Patent Document 2 reports that a scattering layer obtained by spin coating is used to contain an acrylic resin solution containing zinc oxide as scattering particles. Furthermore, the subject of Patent Document 3 reports: a sol-gel solution of a hydrolyzate of tetraethoxy decane, and a particle diameter A mixture of an 80 nm cerium oxide sol solution was applied by spin coating, and a hardened film obtained by heating at 300 ° C was used as a scattering layer.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：國際公開第2009/116531號 Patent Document 1: International Publication No. 2009/116531

專利文獻2：日本專利特開2010-182449號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-182449

專利文獻3：國際公開第2003/26357號 Patent Document 3: International Publication No. 2003/26357

然而，專利文獻1所記載的散射層，因為藉由使玻璃料熔融而形成，因而必需依500℃以上的溫度施行煅燒，所以會有熱能的消耗量較多、且需要高溫煅燒爐等生產性的問題。又，因為需要高溫下的煅燒，因而會有塑膠材無法使用為基板等的問題，導致通用性差。又，因為該散射膜係屬於無機玻璃材質，因而判斷可撓性較低，因而會有無法適用於超薄板玻璃與塑膠薄膜所代表之具可撓性基板材料(以下稱「可撓性基板材料」)的問題。 However, since the scattering layer described in Patent Document 1 is formed by melting a glass frit, it is necessary to perform calcination at a temperature of 500 ° C or higher. Therefore, the amount of thermal energy consumed is large, and productivity such as a high-temperature calcination furnace is required. The problem. Moreover, since calcination at a high temperature is required, there is a problem that a plastic material cannot be used as a substrate or the like, resulting in poor versatility. In addition, since the scattering film is made of an inorganic glass material, it is judged that the flexibility is low, and thus it is not suitable for a flexible substrate material represented by ultra-thin glass and plastic film (hereinafter referred to as "flexible substrate". Material") problem.

專利文獻2所記載的散射層係將樹脂溶液利用旋塗施行塗佈而形成。經塗佈後，藉由依溶劑沸點程度的溫度施行乾燥便可形成散射層，因為熱能消耗量較少，因而屬較佳。但是，形成的散射膜係以有機樹脂為主成分，因而耐熱溫度較低。所以，當使用為會經由溫度變化較大製程的電子裝置用基板時會出現問題。又，有機樹脂的折射率一般係1.5~1.6左右的較低程度，例如使用為有機EL的基板時， 則在與鄰接高折射體的ITO膜(折射率1.9)之界面處，發光光的全反射仍然較大，光取出效率的改善尚嫌不足。 The scattering layer described in Patent Document 2 is formed by applying a resin solution by spin coating. After coating, the scattering layer can be formed by drying at a temperature depending on the boiling point of the solvent, which is preferred because it consumes less heat. However, the formed scattering film is mainly composed of an organic resin, and thus the heat resistant temperature is low. Therefore, problems occur when using a substrate for an electronic device which is subjected to a process with a large temperature change. Further, the refractive index of the organic resin is generally low to about 1.5 to 1.6, for example, when a substrate which is an organic EL is used, Then, at the interface with the ITO film (refractive index of 1.9) adjacent to the high refractive body, the total reflection of the luminescent light is still large, and the improvement of the light extraction efficiency is insufficient.

專利文獻3所記載的散射層係藉由塗佈金屬烷氧化物的溶膠-凝膠液而形成。與專利文獻2同樣均屬於利用塗佈施行的輕易形成方法，又就從可獲得具有高耐熱性膜的觀點，可為屬較佳方法。然而，由金屬烷氧化物的溶膠-凝膠液所形成之硬化膜，若膜厚變厚，會因硬化時的收縮應力而發生龜裂(crack)。不會發生龜裂的有效膜厚係200nm以下(作花濟夫、表面技術2006年57號)，因為要在有效膜厚中導入對可見光散射屬有效粒徑數十nm以上散射粒子的量便有限定，會有導致當作光散射膜時的機能差之情況。又，因為該散射膜係屬於無機玻璃材質，因而會有可撓性低、無法適用於可撓性基板材料的問題。 The scattering layer described in Patent Document 3 is formed by applying a metal alkoxide sol-gel solution. Similarly to Patent Document 2, it is an easy formation method by coating, and it is a preferable method from the viewpoint of obtaining a film having high heat resistance. However, when the film thickness is increased by the sol-gel solution of the metal alkoxide, the cured film is cracked by the shrinkage stress at the time of hardening. The effective film thickness of the crack does not occur is 200 nm or less (for Huaqifu, Surface Technology No. 57, 2006), because the amount of scattering particles having an effective particle diameter of several tens of nm or more for visible light scattering is introduced into the effective film thickness. There is a limit, and there is a case where the function as a light scattering film is poor. Further, since the scattering film is made of an inorganic glass material, there is a problem that flexibility is low and it is not suitable for use in a flexible substrate material.

本發明目的在於提供：利用塗佈等便可輕易形成的塗佈用組成物，以及提供：耐熱性、表面平滑性、可撓性均優異，且具有高折射率、光散射性及光線穿透率的多孔質膜、光散射膜及有機電場發光元件。 An object of the present invention is to provide a coating composition which can be easily formed by coating or the like, and which provides excellent heat resistance, surface smoothness, and flexibility, and has high refractive index, light scattering property, and light penetration. A porous film, a light-scattering film, and an organic electric field light-emitting element.

本發明者係有鑑於上述問題經深入鑽研的結果，發現在由含有聚矽烷、金屬氧化物及溶劑的組成物經硬化，而獲得硬化物的內部會形成空隙。發現有形成空隙的多孔質硬化物，因為具有光散射特性，因而可應用為光散射膜，遂完成本發明。 The inventors of the present invention have intensively studied in view of the above problems, and found that voids are formed in a portion obtained by curing a composition containing polydecane, a metal oxide, and a solvent to obtain a cured product. It has been found that a porous cured product having voids can be used as a light-scattering film because of its light-scattering property, and the present invention has been completed.

即，本發明係如下所示。 That is, the present invention is as follows.

[1]一種塗佈用組成物，係含有聚矽烷化合物、金屬氧化物及溶劑。 [1] A coating composition comprising a polydecane compound, a metal oxide, and a solvent.

[2]如上述[1]所記載的塗佈用組成物，其中更進一步含有具胺基甲酸酯結構的化合物。 [2] The coating composition according to the above [1], which further comprises a compound having a urethane structure.

[3]如上述[2]所記載的塗佈用組成物，其中，上述具有胺基甲酸酯結構的化合物係分散劑。 [3] The coating composition according to the above [2], wherein the compound having a urethane structure is a dispersant.

[4]如上述[1]~[3]項中任一項所記載的塗佈用組成物，其中，上述金屬氧化物係從氧化鋅、氧化鈦、鈦酸鋇、氧化鉭、氧化矽、氧化鋁、氧化鋯、氧化鈰、及氧化錫中選擇至少1種。 The coating composition according to any one of the above aspects, wherein the metal oxide is derived from zinc oxide, titanium oxide, barium titanate, cerium oxide, cerium oxide, or the like. At least one selected from the group consisting of alumina, zirconia, cerium oxide, and tin oxide.

[5]如上述[1]~[4]項中任一項所記載的塗佈用組成物，其中，上述金屬氧化物的折射率係2.0以上。 The coating composition according to any one of the above aspects, wherein the metal oxide has a refractive index of 2.0 or more.

[6]如上述[1]~[5]項中任一項所記載的塗佈用組成物，其中，上述金屬氧化物的平均粒徑係1000nm以下。 The coating composition according to any one of the above aspects, wherein the metal oxide has an average particle diameter of 1000 nm or less.

[7]如上述[1]~[6]項中任一項所記載的塗佈用組成物，其中，上述聚矽烷化合物係一般式(2)所示矽網絡聚合物：(R²Si)_n‧‧‧(2)(式(2)中，R²係顯示相同或不同的氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基、酚性羥基或胺基。n係4~10000的整數。) The coating composition according to any one of the above aspects, wherein the polydecane compound is a fluorene network polymer represented by the general formula (2): (R ² Si). _n ‧‧‧(2) (In the formula (2), R ² shows the same or different hydrogen atom, alkyl group, alkenyl group, arylalkyl group, aryl group, alkoxy group, hydroxyl group, phenolic hydroxyl group or amine Base. n is an integer from 4 to 10000.)

[8]一種多孔質膜，係藉由使上述[1]~[7]項中任一項所記載的塗佈用組成物硬化而獲得。 [8] A porous film obtained by curing the coating composition according to any one of the items [1] to [7] above.

[9]一種光散射膜，係藉由使上述[1]~[7]項中任一項所記載的塗佈用組成物硬化而獲得。 [9] A light-scattering film obtained by curing the coating composition according to any one of the above [1] to [7].

[10]一種有機電場發光元件，係含有上述[9]所記載的光散射膜。 [10] An organic electroluminescence device comprising the light-scattering film according to [9] above.

[11]如上述[10]所記載的有機電場發光元件，其中，上述光散射膜係配 置於基板與陽極之間。 [11] The organic electroluminescence device according to [10] above, wherein the light scattering film is coupled Placed between the substrate and the anode.

[12]如上述[11]所記載的有機電場發光元件，其中，上述基板係具可撓性的可撓性基板。 [12] The organic electroluminescence device according to the above [11], wherein the substrate is a flexible flexible substrate.

[13]一種有機EL顯示裝置，係含有上述[10]~[12]項中任一項所記載的有機電場發光元件。 [13] An organic EL display device according to any one of the items [10] to [12] above.

[14]一種有機EL照明，係含有上述[10]~[12]項中任一項所記載的有機電場發光元件。 [14] An organic EL illumination device according to any one of the items [10] to [12] above.

[15]一種多孔質膜之製造方法，係將上述[1]~[7]項中任一項所記載的塗佈用組成物塗佈於基板上，再去除溶劑。 [15] A method for producing a porous film, which is characterized in that the coating composition according to any one of the above [1] to [7] is applied onto a substrate, and the solvent is removed.

根據本發明，利用塗佈等簡便方法便可形成光散射層。又，所獲得光散射層係耐熱性優異、具有高折射率、且表面平滑性優異、具有高光散射性與高光線穿透率。 According to the present invention, a light scattering layer can be formed by a simple method such as coating. Further, the obtained light-scattering layer is excellent in heat resistance, has a high refractive index, is excellent in surface smoothness, and has high light-scattering property and high light transmittance.

1‧‧‧電洞注入層 1‧‧‧ hole injection layer

2‧‧‧電洞輸送層 2‧‧‧ hole transport layer

3‧‧‧發光層 3‧‧‧Lighting layer

4‧‧‧電子注入層 4‧‧‧Electronic injection layer

5‧‧‧陰極 5‧‧‧ cathode

6‧‧‧陽極(ITO) 6‧‧‧Anode (ITO)

7‧‧‧散射膜(光取出膜) 7‧‧‧scattering film (light extraction film)

8‧‧‧基板(玻璃基板) 8‧‧‧Substrate (glass substrate)

9‧‧‧開口堤(堤材) 9‧‧‧Open dike (dike)

10‧‧‧薄片狀脫水材 10‧‧‧Flake-shaped dehydrated material

11‧‧‧錐坑玻璃 11‧‧‧ cone glass

12‧‧‧光硬化性樹脂 12‧‧‧Photocurable resin

100‧‧‧有機電解發光元件 100‧‧‧Organic Electroluminescent Element

圖1係散射層1的表面之SEM影像(1萬倍)照片。 Fig. 1 is a photograph of an SEM image (10,000 times) of the surface of the scattering layer 1.

圖2係散射層1的截面之SEM影像(3萬倍)照片。 2 is a SEM image (30,000 times) of a cross section of the scattering layer 1.

圖3係散射層16的表面之SEM影像(1萬倍)照片。 3 is a SEM image (10,000 times) photograph of the surface of the scattering layer 16.

圖4係散射層17的表面之SEM影像(1萬倍)照片。 4 is a SEM image (10,000 times) photograph of the surface of the scattering layer 17.

圖5係有機電場發光元件的構造一例概略圖。 Fig. 5 is a schematic view showing an example of a structure of an organic electric field light-emitting element.

圖6係有機電場發光元件的構造一例概略圖。 Fig. 6 is a schematic view showing an example of a structure of an organic electric field light-emitting element.

以下，針對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.

I.塗佈用組成物 I. Coating composition

本發明的塗佈用組成物係含有聚矽烷化合物、金屬氧化物及溶劑。 The coating composition of the present invention contains a polydecane compound, a metal oxide, and a solvent.

(1)聚矽烷化合物 (1) Polydecane compounds

所謂「聚矽烷化合物」係具有如下所示矽(Si)-矽(Si)鍵結的化合物總稱，在Si-Si鍵結主鏈上因為σ鍵結呈非局部化，因而具有高折射率、可見光穿透性優異。本發明所使用的聚矽烷化合物係在如下述所例示具有Si-Si鍵結的直鏈狀、環狀、網絡狀化合物之前提下，其餘並無特別的限制。 The "polydecane compound" is a general term for a compound having a 矽(Si)-矽(Si) bond as shown below, and has a high refractive index because the sigma bond is non-localized in the Si-Si bond main chain. Excellent visible light penetration. The polydecane compound used in the present invention is provided before the linear, cyclic or network-like compound having Si-Si bond as exemplified below, and the rest is not particularly limited.

(1)-1：直鏈狀聚矽烷化合物及環狀聚矽烷化合物 (1)-1: linear polydecane compound and cyclic polydecane compound

(R¹ ₂Si)_m‧‧‧(1)(式(1)中，R¹係表示氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基、酚性羥基或胺基。R¹係可全部均相同、或亦可任意組合上述所記載取代基。m係2~10000的整數。) (R ¹ ₂ Si) _m ‧‧‧(1) (In the formula (1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, a hydroxyl group, or a phenolic hydroxyl group. Or an amine group. The R ¹ group may be all the same or may be arbitrarily combined with the substituents described above. m is an integer of 2 to 10000.)

(1)-2：矽網絡聚合物 (1)-2: 矽 network polymer

(R²Si)_n‧‧‧(2)(式(2)中，R²係表示相同或不同的氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基、酚性羥基或胺基。n係4~10000的整數。) (R ² Si) _n ‧‧‧(2) (In the formula (2), R ² represents the same or different hydrogen atom, alkyl group, alkenyl group, arylalkyl group, aryl group, alkoxy group, hydroxyl group, Phenolic hydroxyl or amine group. n is an integer from 4 to 10000.)

(1)-3：網絡狀聚合物 (1)-3: Network polymer

(R³ ₂Si)_x(R³Si)_ySi_z‧‧‧(3)(式(3)中，R³係表示氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、 羥基、酚性羥基或胺基。R³係可全部均相同、或亦可任意組合上述所記載取代基。x、y及z係0以上的整數，且x、y及z的和係5~10000，但x、y及z中任二者為0的情況除外。) (R ³ ₂ Si) _x (R ³ Si) _y Si _z ‧‧‧(3) (In the formula (3), R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group or an alkane An oxy group, a hydroxyl group, a phenolic hydroxyl group or an amine group. The R ³ groups may all be the same or may be arbitrarily combined with the substituents described above. x, y and z are integers of 0 or more, and the sum of x, y and z It is 5~10000, except when x, y and z are both 0.)

上述聚合物係可利用下述方法進行製造，該等方法係例如：以具有各自結構單元的單體為原料，例如在鹼金屬存在下，使鹵矽烷類進行脫鹵縮聚的方法(「封鏈法」J.Am.Chem.Soc.、110、124(1988)、Macromolecules、23、3423(1990))；利用電極還原使鹵矽烷類進行脫鹵縮聚的方法(J.Chem.Soc.、Chem.Commun.、1161(1990)、J.Chem.Soc.、Chem.Commun.、897(1992))；在金屬觸媒存在下使氫化矽烷類進行脫氫縮聚的方法(日本專利特開平4-334551號公報)；由利用聯苯等進行交聯的二矽烯，施行陰離子聚合的方法(Macromolecules、23、4494(1990))；以及利用環狀矽烷類的開環聚合而進行之方法等。 The above-mentioned polymer can be produced by a method in which, for example, a monomer having a respective structural unit is used as a raw material, for example, a halogenated condensed product is subjected to dehalogenation and polycondensation in the presence of an alkali metal ("chain sealing" J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 23, 3423 (1990)); Method for dehalogenation and polycondensation of halodecane by electrode reduction (J. Chem. Soc., Chem .Commun., 1161 (1990), J. Chem. Soc., Chem. Commun., 897 (1992)); a method for dehydrogenating polycondensation of hydrogenated decanes in the presence of a metal catalyst (Japanese Patent Laid-Open 4- JP-A No. 334551), a method in which an anion polymerization is carried out by dioxene which is crosslinked by biphenyl or the like (Macromolecules, 23, 4494 (1990)); and a method in which ring-opening polymerization using a cyclic decane is carried out.

一般式(1)所示直鏈狀聚矽烷化合物及環狀聚矽烷化合物，R¹較佳係相同或不同的氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基，更佳係氫原子、烷基、芳基、烷氧基、羥基。又，m較佳係2~300、更佳係4~150。較佳係例如平均聚合度4~150的甲基苯基聚矽烷。 The linear polydecane compound represented by the formula (1) and the cyclic polydecane compound, and R ^{1 is} preferably the same or different hydrogen atom, alkyl group, alkenyl group, arylalkyl group, aryl group or alkoxy group. The hydroxyl group is more preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a hydroxyl group. Further, m is preferably 2 to 300, more preferably 4 to 150. Preferred are, for example, methylphenylpolydecane having an average degree of polymerization of from 4 to 150.

一般式(2)所示矽網絡聚合物，R²較佳係相同或不同的氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基，更佳係氫原子、烷基、芳基、烷氧基、羥基。又，R²係由烷基及苯基構成；烷基較佳係甲基，芳基較佳係苯基。又，n較佳係4~300、更佳係4~150。較佳 係例如平均聚合度4~150的苯基網絡聚矽烷。 In general, the network polymer of the formula (2), R ^{2 is} preferably the same or different hydrogen atom, alkyl group, alkenyl group, arylalkyl group, aryl group, alkoxy group, hydroxyl group, more preferably a hydrogen atom, Alkyl, aryl, alkoxy, hydroxy. Further, R ² is composed of an alkyl group and a phenyl group; the alkyl group is preferably a methyl group, and the aryl group is preferably a phenyl group. Further, n is preferably 4 to 300, more preferably 4 to 150. Preferred are, for example, phenyl network polydecane having an average degree of polymerization of from 4 to 150.

一般式(3)所示以Si-Si鍵結為骨架的網絡狀聚合物，R³較佳係相同或不同的氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基，更佳係氫原子、烷基、芳基、烷氧基、羥基。又，R³係由芳基構成；芳基更佳係由苯基構成。又，x、y及z分別較佳係1~300、1~300及1~50。 A network polymer having a Si-Si bond as a skeleton represented by the general formula (3), and R ^{3 is} preferably the same or different hydrogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group or an alkoxy group. More preferably, the hydroxyl group is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group or a hydroxyl group. Further, R ³ is composed of an aryl group; and the aryl group is more preferably composed of a phenyl group. Further, x, y, and z are preferably 1 to 300, 1 to 300, and 1 to 50, respectively.

就從具有較高耐熱性的觀點，聚矽烷化合物的結構較佳係使用一般式(2)或一般式(3)的聚合物。 From the viewpoint of having higher heat resistance, the structure of the polydecane compound is preferably a polymer of the general formula (2) or the general formula (3).

較佳的聚矽烷化合物係可例如大阪瓦斯化學(股)製OGSOL® SI-10-10、SI-10-20、SI-20-10、SI-20-10(改)、SI-30-10等。其中，較佳係使用SI-20-10(改)。 Preferred polydecane compounds are, for example, OGSOL® SI-10-10, SI-10-20, SI-20-10, SI-20-10 (modified), SI-30-10 manufactured by Osaka Gas Chemical Co., Ltd. Wait. Among them, it is preferable to use SI-20-10 (modified).

另外，SI-20-10(改)係重量平均分子量(Mw)1200、數量平均分子量(Mn)900(GPC：聚苯乙烯換算)，耐熱溫度354℃(5%重量減)，且具有末端羥基的甲基苯基聚矽烷化合物(甲基：苯基=約1：3莫耳比)。上述甲基苯基聚矽烷推測苯基比率較低，更容易形成空隙。甲基苯基聚矽烷化合物的甲基：苯基(莫耳比)係1：9以下、較佳係1：5以下、更佳係1：3以下。本發明中，上述聚矽烷化合物分別可單獨使用，或者亦可併用2種以上。又，當併用2種以上的聚矽烷化合物時，該等的混合比例並無特別的限制，可任意選擇。 Further, SI-20-10 (modified) is a weight average molecular weight (Mw) of 1200, a number average molecular weight (Mn) of 900 (GPC: polystyrene), a heat resistant temperature of 354 ° C (5% by weight), and has a terminal hydroxyl group. Methylphenyl polydecane compound (methyl: phenyl = about 1:3 molar ratio). The above methylphenyl polydecane has a lower phenyl ratio and is more likely to form voids. The methyl group of the methylphenyl polydecane compound: phenyl (mole ratio) is 1:9 or less, preferably 1:5 or less, more preferably 1:3 or less. In the present invention, the polydecane compounds may be used singly or in combination of two or more kinds. In addition, when two or more kinds of polydecane compounds are used in combination, the mixing ratio is not particularly limited and may be arbitrarily selected.

(2)金屬氧化物 (2) Metal oxides ‧金屬氧化物的種類 ‧Types of metal oxides

本發明的塗佈組成物係含有當作金屬氧化物用的金屬氧化物粒子。金屬氧化物粒子係就從屬於高耐熱性的觀點頗適於使用。此種金屬氧化物粒子係可舉例如：氧化鋅、氧化鈦、氧化矽、氧化鋁、氧化鋯、氧化鈰、氧化錫、氧化鉭、氧化銅、氧化銀、氧化鐵、氧化鉍、氧化鎢、氧化銦、氧化錳、氧化釩、氧化鈮、鈦酸鍶、鈦酸鋇、銦-錫氧化物(ITO)、鋁-鋅氧化物(AZO)、鎵-鋅氧化物(GZO)等。該等均屬於公知物質，可輕易容易。又，其原料、製造方法等並無特別的限制。此時，金屬氧化物粒子亦可經施行表面處理。表面處理的方法係可例如：在金屬氧化物粒子粉體中添加表面處理劑，再使用球磨機、珠磨機、混練機等施行均勻混合，或者併用加熱處理等，而使金屬氧化物粒子上吸附著表面處理劑、或化學性鍵結的方法等。利用表面處理而被導入的化學物種係可舉例如：氫氧化鋁、二氧化矽、氧化鋯等無機氧化物；硬脂酸等有機酸；磷酸等無機酸；氨及胺等鹼性化學物種；聚矽氧等。 The coating composition of the present invention contains metal oxide particles as a metal oxide. The metal oxide particle system is suitable for use from the viewpoint of high heat resistance. Examples of such metal oxide particles include zinc oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, cerium oxide, tin oxide, cerium oxide, copper oxide, silver oxide, iron oxide, cerium oxide, and tungsten oxide. Indium oxide, manganese oxide, vanadium oxide, cerium oxide, barium titanate, barium titanate, indium-tin oxide (ITO), aluminum-zinc oxide (AZO), gallium-zinc oxide (GZO), and the like. These are all known substances and can be easily and easily. Moreover, the raw material, the manufacturing method, and the like are not particularly limited. At this time, the metal oxide particles may also be subjected to surface treatment. The surface treatment method may be, for example, adding a surface treatment agent to the metal oxide particle powder, and performing uniform mixing using a ball mill, a bead mill, a kneading machine, or the like, or a heat treatment or the like to adsorb the metal oxide particles. A surface treatment agent, or a method of chemical bonding, or the like. Examples of the chemical species introduced by the surface treatment include inorganic oxides such as aluminum hydroxide, ceria, and zirconia; organic acids such as stearic acid; inorganic acids such as phosphoric acid; and basic chemical species such as ammonia and amine; Polyoxane, etc.

本發明中，可將金屬氧化物粒子單獨混合於組成物中、或亦可混合2種以上。混合比例並無特別的限制，可任意選擇。又，混合時，金屬氧化物粒子可依粉體進行混合，亦可預先使分散於適當溶劑中之後，經形成分散液之後才進行混合。金屬氧化物粒子較佳係氧化鋅、氧化鈦、鈦酸鋇、氧化鉭、氧化矽、氧化鋁、氧化鋯、氧化鈰、氧化錫。理由係可見光線的吸收較小，可獲得高可見光線穿透率。金屬氧化物的折射率較佳係2.0以上。理由係當在有機電場發光元件中利用為提高光取出效率的散射膜時，若較高於相鄰接高折射體之ITO 膜(折射率約1.9)的折射率時，便不會因因界面處的全反射而發生光損失。折射率達2.0以上的金屬氧化物，係可例如：氧化鈦、氧化鋅、氧化鈰、鈦酸鋇、氧化鋯、氧化鉭、氧化鎢、氧化錫、氧化銦等。 In the present invention, the metal oxide particles may be mixed alone or in combination of two or more kinds. The mixing ratio is not particularly limited and can be arbitrarily selected. Further, at the time of mixing, the metal oxide particles may be mixed according to the powder, or may be mixed after being dispersed in a suitable solvent and then formed into a dispersion. The metal oxide particles are preferably zinc oxide, titanium oxide, barium titanate, cerium oxide, cerium oxide, aluminum oxide, zirconium oxide, cerium oxide or tin oxide. The reason is that the absorption of visible light is small, and high visible light transmittance can be obtained. The refractive index of the metal oxide is preferably 2.0 or more. The reason is that when a scattering film for improving the light extraction efficiency is used in the organic electroluminescent element, if it is higher than the adjacent high refractive body ITO When the refractive index of the film (refractive index is about 1.9), light loss does not occur due to total reflection at the interface. The metal oxide having a refractive index of 2.0 or more may be, for example, titanium oxide, zinc oxide, cerium oxide, barium titanate, zirconium oxide, cerium oxide, tungsten oxide, tin oxide or indium oxide.

‧粒徑 ‧particle size

一般微粒子就從外觀上的幾何學形態判斷，可分類為被認為係單位粒子的一次粒子、以及由一次粒子複數個集合的二次粒子。本發明的粒子係一次粒子、二次粒子均可，金屬氧化物粒子的平均粒徑係1000nm以下、較佳係700nm以下、更佳係500nm以下。藉由使用具有此種範圍平均粒徑的金屬氧化物粒子，便可獲得光散射性、光穿透性及表面平坦性均優異的散射膜。另外，金屬氧化物粒子的平均粒徑係當分散液的情況，可依動態光散射方式進行測定。經硬化而獲得光散射膜時，可從電子顯微鏡等的拍攝影像之粒子大小進行計算。 Generally, the microparticles are judged from the geometrical appearance of the appearance, and can be classified into a primary particle which is considered to be a unit particle, and a secondary particle which is a plurality of primary particles. The particles of the present invention may be primary particles or secondary particles, and the average particle diameter of the metal oxide particles is 1000 nm or less, preferably 700 nm or less, more preferably 500 nm or less. By using metal oxide particles having such a range average particle diameter, a scattering film excellent in light scattering property, light transmittance, and surface flatness can be obtained. Further, the average particle diameter of the metal oxide particles is measured as a dispersion liquid by a dynamic light scattering method. When the light-scattering film is obtained by hardening, it can be calculated from the particle size of a captured image of an electron microscope or the like.

該等金屬氧化物微粒子係可利用例如：BYK Japan公司製氧化鋅粒子分散液「NANOBYK3821」(一次粒徑20nm)、「NANOBYK3841」(一次粒徑40nm)、「NANOBYK3842」(一次粒徑40nm)、氧化矽粒子分散液「NANOBYK3650」(一次粒徑20nm)、氧化鋁粒子分散液「NANOBYK3601」(一次粒徑40nm)、「NANOBYK3610」(一次粒徑20nm)、氧化銫粒子分散液「NANOBYK3812」(一次粒徑10nm)；CIK奈米科技公司製氧化鋯粒子分散液「ZRPMAl5WT%-E05」(一次粒徑20nm)、「ZEMIBK15WT%-F57」(一次粒徑10nm)、氧化鈦粒子分散液「PTIMA30WT%-NO1」(一次粒徑250nm)；ULVAC Materials 公司製「ITO Nanometalink ITO1 Cden」；巴製作所公司製「ITO奈米粒子」(標準粒徑：15~25nm)、「ITO奈米粒子」(單一奈米粒徑：5~10nm)、「ITO奈米粒子」(大型奈米粒徑：80~100nm)；奧野製藥公司製ITO奈米粒子「奈米分散機ITO(SP2)」(一次粒徑5~15nm)；日揮觸媒化成公司製TiO₂奈米粒子「PST18NR」(一次粒徑18nm)、「PST400C」(一次粒徑400nm)；Solarnix公司製「Solanix T」(一次粒徑10nm)、「Solanix D20」(一次粒徑20nm)；石原產業製氧化鈦粉體「TTO-55」(一次粒徑30~50nm)、「TTO-51」(一次粒徑10~30nm)；武藏野電子工業製「氧化鈰」粉體、高純度化學製「氧化鉭」粉體等。 For the metal oxide fine particles, for example, a zinc oxide particle dispersion "NANOBYK3821" (primary particle diameter: 20 nm), "NANOBYK3841" (primary particle diameter: 40 nm), and "NANOBYK3842" (primary particle diameter: 40 nm), which are made of BYK Japan, can be used. Yttrium oxide particle dispersion "NANOBYK3650" (primary particle size 20nm), alumina particle dispersion "NANOBYK3601" (primary particle size 40nm), "NANOBYK3610" (primary particle size 20nm), cerium oxide particle dispersion "NANOBYK3812" (once Particle size: 10 nm); Zirconium zirconia particle dispersion "ZRPMAl5WT%-E05" (primary particle size: 20 nm), "ZEMIBK15WT%-F57" (primary particle size: 10 nm), titanium oxide particle dispersion "PTIMA30WT%"-NO1" (primary particle size: 250 nm); "ITO Nanometalink ITO1 Cden" manufactured by ULVAC Materials Co., Ltd.; "ITO nanoparticle" (standard particle size: 15 to 25 nm) and "ITO nanoparticle" manufactured by Bazaar Co., Ltd. Rice particle size: 5~10nm), "ITO nanoparticle" (large nanometer particle size: 80~100nm); ITO nanoparticle manufactured by Okuno Pharmaceutical Co., Ltd. "Nano disperser ITO (SP2)" (primary particle size 5 ~15nm); TiO ₂ nanoparticles produced by the company PST18NR" (primary particle size 18nm), "PST400C" (primary particle size 400nm); "Solanix T" manufactured by Solarix Company (primary particle size 10nm), "Solanix D20" (primary particle size 20nm); "TTO-55" (primary particle size 30~50nm), "TTO-51" (primary particle size 10~30nm); "铈 铈" powder made by Musashino Electronics Industry, high-purity chemical "yttrium oxide" powder Body and so on.

(3)溶劑 (3) Solvent

本發明塗佈用組成物中所含的溶劑，係在會分散或溶解聚矽烷化合物及金屬氧化物，並可塗佈之前提下，其餘並無特別的限制。可例如：甲苯、二甲苯、茴香醚等芳香族溶劑；四氫呋喃、丙二醇單甲醚等醚類；甲乙酮、甲基異丁酮、環己酮等酮類；丙二醇單甲醚醋酸酯、醋酸賽珞蘇、乳酸乙酯等酯類；二氯甲烷、單氯苯等鹵化烴類；N-甲基吡咯啶酮等雜環類等。該等可單獨使用、亦可使用2種以上的混合溶劑。 The solvent contained in the coating composition of the present invention is obtained by dispersing or dissolving a polydecane compound and a metal oxide, and can be removed before coating, and the rest is not particularly limited. For example, an aromatic solvent such as toluene, xylene or anisole; an ether such as tetrahydrofuran or propylene glycol monomethyl ether; a ketone such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; propylene glycol monomethyl ether acetate; Esters such as sulphate and ethyl lactate; halogenated hydrocarbons such as dichloromethane and monochlorobenzene; and heterocyclic hydrocarbons such as N-methylpyrrolidone. These may be used singly or in combination of two or more kinds.

本發明中，上述塗佈用組成物較佳係更進一步含有具胺基甲酸酯結構的化合物(以下稱「胺基甲酸酯化合物」)。 In the present invention, the coating composition preferably further contains a compound having a urethane structure (hereinafter referred to as "urethane compound").

(4)胺基甲酸酯化合物 (4) urethane compounds

本發明塗佈用組成物的特點係在經硬化而獲得硬化物的內部會形 成空隙。雖會形成空隙的機制尚未明朗，但可推測在溶劑被乾燥除去的過程中，金屬氧化物粒子與聚矽烷化合物的混合物會一邊與溶劑進行相分離、一邊進行凝聚、結合，而形成空隙。此時，組成物中的胺基甲酸酯化合物(所有具有胺甲酸乙酯鍵結的化合物)係具有促進空隙形成的效果。組成物中的胺基甲酸酯化合物係在加熱硬化的過程中會熱分解而生成二氧化碳、氮等分解氣體，該分解氣體會在硬化中的組成物中形成氣泡並內含，判斷藉此對空隙的形成具有貢獻。若利用掃描式電子顯微鏡觀察硬化物的截面，在空隙的外周部分發現有微粒子。若對該微粒子施行EDX(能量散佈式X射線分光法)分析，便檢測到主成分為C(碳)元素。該碳的微粒子可認為係因某有機物進行熱分解而碳化生成者，證實分解氣體的生成會有參與空隙形成機制的可能性。 The coating composition of the present invention is characterized in that it is hardened to obtain a cured interior. Become a gap. Although the mechanism for forming voids is not clear, it is presumed that during the process in which the solvent is dried and removed, the mixture of the metal oxide particles and the polydecane compound is agglomerated and bonded while being phase-separated from the solvent to form voids. At this time, the urethane compound (all compounds having an urethane bond) in the composition has an effect of promoting void formation. The urethane compound in the composition is thermally decomposed during heat hardening to form a decomposition gas such as carbon dioxide or nitrogen, and the decomposition gas forms bubbles in the hardened composition and is contained therein. The formation of voids contributes. When the cross section of the cured product is observed by a scanning electron microscope, fine particles are found in the outer peripheral portion of the void. When EDX (energy dispersive X-ray spectroscopy) analysis was performed on the fine particles, the main component was detected as a C (carbon) element. The fine particles of carbon are considered to be carbonized by the thermal decomposition of an organic substance, and it is confirmed that the formation of the decomposition gas may participate in the mechanism of void formation.

胺基甲酸酯化合物較佳係當作分散劑並含於組成物中。當進行為從金屬氧化物粉體獲得分散液的分散處理時，可使用胺基甲酸酯化合物的分散劑製備分散液，亦可對使用胺基甲酸酯化合物以外的分散劑之分散液，在之後才追加添加胺基甲酸酯化合物的分散劑。任一情況均可獲得促進空隙形成的效果。具有胺基甲酸酯結構的分散劑係可舉例如：BYK Japan公司製「DisperBYK-9077」、同「DisperBYK-9076」、同「DisperBYK-163」、同「DisperBYK-164」、同「DisperBYK-2163」、同「DisperBYK-2164」、同「DisperBYK-2155」、Evonik Degussa公司製「TEGO Dispers710」等。使用具有胺基甲酸酯結構之分散劑的金屬氧化物分散液，係可舉例如：BYK Japan公司製氧化鋅粒子分散液「NANOBYK-3821」(一次粒徑20nm)、 「NANOBYK-3841」(一次粒徑40nm)、氧化矽粒子分散液「NANOBYK-3650」(一次粒徑20nm)、氧化鋁粒子分散液「NANOBYK-3601」(一次粒徑40nm)等。胺基甲酸酯化合物係相對於上述組成物中的金屬氧化物與聚矽烷之固形份重量合計為0.01%~50%、較佳係0.05%~30%、更佳係0.1%~20%。若在此範圍內，便具有為促進空隙形成用的足夠量，不會使對散射膜所要求的膜特性出現明顯降低。 The urethane compound is preferably used as a dispersing agent and is contained in the composition. When the dispersion treatment for obtaining the dispersion liquid from the metal oxide powder is carried out, a dispersion liquid may be prepared using a dispersant of a urethane compound, or a dispersion liquid using a dispersant other than the urethane compound may be used. The dispersing agent to which the urethane compound is added is added later. The effect of promoting void formation can be obtained in either case. The dispersing agent having a urethane structure may, for example, be "DisperBYK-9077" manufactured by BYK Japan Co., Ltd., "DisperBYK-9076", "DisperBYK-163", "DisperBYK-164", and "DisperBYK-". 2163", "DisperBYK-2164", "DisperBYK-2155", and "TEGO Dispers710" manufactured by Evonik Degussa. For the metal oxide dispersion liquid having a dispersant having a urethane structure, for example, a zinc oxide particle dispersion "NANOBYK-3821" (primary particle diameter: 20 nm) manufactured by BYK Japan Co., Ltd., "NANOBYK-3841" (primary particle diameter: 40 nm), cerium oxide particle dispersion "NANOBYK-3650" (primary particle diameter: 20 nm), alumina particle dispersion "NANOBYK-3601" (primary particle diameter: 40 nm), and the like. The urethane compound is 0.01% to 50%, preferably 0.05% to 30%, more preferably 0.1% to 20%, based on the total weight of the metal oxide and the polydecane in the above composition. If it is within this range, it has a sufficient amount for promoting the formation of voids, and does not significantly reduce the film properties required for the scattering film.

(5)塗佈用組成物之製備 (5) Preparation of coating composition

上述組成物中，金屬氧化物與聚矽烷化合物的混合比係99：1~1：99、較佳係95：5~30：70、更佳係90：10~40：60。如前述，在由本發明組成物硬化而獲得之硬化物中會有空隙形成。該空隙推測係在溶劑被乾燥除去的過程中，金屬氧化物粒子與聚矽烷化合物的混合物會一邊與溶劑相分離，一邊內含氣泡並凝聚、結合，而形成空隙的緣故，若在上述混合比便會順暢地進行相分離、氣泡內含、凝聚、結合等，俾可輕易地調整空隙直徑、空隙率控制。 In the above composition, the mixing ratio of the metal oxide to the polydecane compound is 99:1 to 1:99, preferably 95:5 to 30:70, more preferably 90:10 to 40:60. As described above, voids are formed in the cured product obtained by hardening the composition of the present invention. This void is presumed to be a process in which the mixture of the metal oxide particles and the polydecane compound is separated from the solvent while the solvent is separated from the solvent, and agglomerates and bonds to form a void. The phase separation, bubble inclusion, agglomeration, bonding, and the like are smoothly performed, and the void diameter and void ratio control can be easily adjusted.

在組成物製備之際，可適當選擇：在溶劑中有溶解聚矽烷化合物的溶液中，分散處理金屬氧化物粒子粉體而形成分散液的方法；或使聚矽烷化合物溶解於金屬氧化物粒子分散液中的方法；或金屬氧化物分散液與聚矽烷溶液相混合的方法。就從金屬氧化物微粒子、聚矽烷化合物較容易均勻、且亦較容易獲得組成物保存安定性的觀點，較佳係金屬氧化物分散液與聚矽烷溶液相混合的方法。又，更 佳係金屬氧化物分散液與聚矽烷溶液的溶劑物種為相同。粒子的分散液之製備方法，一般係將溶劑、分散劑及粒子、以及視需要的粉碎用球珠，預先依固形份濃度成為5~70重量%的方式進行混合，經分散處理而製備成粒子分散液。分散處理的方法係可使用例如：利用超音波分散機進行的分散處理、砂磨機、磨碎器、珠粒磨碎機、珠磨機、球磨機、或者利用流化床、高速攪拌機、均質機、塗料攪拌器等進行的分散方法等等任一方法。 In the preparation of the composition, a method of dispersing and treating the metal oxide particle powder to form a dispersion in a solution in which a polydecane compound is dissolved in a solvent; or dissolving the polydecane compound in the dispersion of the metal oxide particles may be appropriately selected. a method in a liquid; or a method in which a metal oxide dispersion is mixed with a polydecane solution. From the viewpoint that the metal oxide fine particles and the polydecane compound are relatively easy to be uniform and the storage stability of the composition is relatively easy to obtain, a method in which the metal oxide dispersion is mixed with the polydecane solution is preferred. Again, more The solvent species of the preferred metal oxide dispersion is the same as that of the polydecane solution. The method for preparing a dispersion of particles is generally prepared by mixing a solvent, a dispersant, and particles, and optionally a ball for pulverization, in a form of 5 to 70% by weight based on the solid content, and preparing the particles by dispersion treatment. Dispersions. The method of the dispersion treatment may be, for example, a dispersion treatment using an ultrasonic disperser, a sand mill, a pulverizer, a bead mill, a bead mill, a ball mill, or a fluidized bed, a high speed mixer, a homogenizer Any method such as a dispersion method by a paint agitator or the like.

為提升粒子的分散安定性，通常分亦可含有當作散劑用之市售低分子分散劑、高分子分散劑。其中，因為具有胺基甲酸酯結構的分散劑亦可期待促進空隙形成的效果，因而屬較佳。 In order to enhance the dispersion stability of the particles, a commercially available low molecular dispersant or a polymer dispersant may be contained as a powder. Among them, a dispersant having a urethane structure is also expected to have an effect of promoting void formation.

高分子分散劑係可舉例如：胺甲酸乙酯系分散劑、聚伸乙亞胺系分散劑、聚氧化伸烷基烷醚系分散劑、聚氧化乙二醇二酯系分散劑、山梨糖醇酐脂肪族酯系分散劑、脂肪族變性聚酯系分散劑等。該等分散劑係可單獨使用、或混合2種以上使用。當含有分散劑時，含有量係分散劑對粒子的含有比例較佳係0.1~50重量%、更佳係0.5~35重量%、特佳係1~30重量%、最佳係2~25重量%。若分散劑對粒子的含有比例低於0.1重量%，會有分散液中的粒子分散安定性變差之可能性，若超過50重量%，則會有散射膜的膜特性降低之可能性。 Examples of the polymer dispersant include an urethane dispersant, a polyethylenimine dispersant, a polyoxyalkylene alkyl dispersant, a polyethylene oxide diester dispersant, and sorbose. An alcoholic anhydride aliphatic ester dispersant, an aliphatic modified polyester dispersant, or the like. These dispersing agents can be used singly or in combination of two or more. When the dispersant is contained, the content ratio of the dispersant to the particles is preferably 0.1 to 50% by weight, more preferably 0.5 to 35% by weight, particularly preferably 1 to 30% by weight, and most preferably 2 to 25% by weight. %. When the content ratio of the dispersant to the particles is less than 0.1% by weight, the dispersion stability of the particles in the dispersion may be deteriorated, and if it exceeds 50% by weight, the film properties of the scattering film may be lowered.

再者，組成物的黏度，就從塗佈性的觀點係0.5mPa‧s~500mPa‧s左右。另外，在組成物中，視需要亦可混合入界面活性劑、流動調整劑、消泡劑等添加物。依此所製備的組成物，將成為依照以下所說明方法形成多孔質膜、散射膜(以下有統稱「膜」的情況) 時的原料。 Further, the viscosity of the composition is from about 0.5 mPa ‧ to 500 mPa ‧ from the viewpoint of coatability. Further, in the composition, an additive such as a surfactant, a flow regulating agent, or an antifoaming agent may be mixed as needed. The composition prepared in accordance with the above will form a porous film or a scattering film according to the method described below (hereinafter collectively referred to as "film") When the raw materials.

II.膜之形成方法 II. Method for forming film

上述塗佈用組成物係塗佈於例如玻璃、塑膠等適當基板上，經去除溶劑便可形成硬化物、即多孔質膜、光散射膜。塗佈方法係可使用例如：旋塗法、浸塗法、模頭塗佈法、棒塗法、刮刀塗佈法、輥塗佈法、噴塗法、毛細管塗佈法、噴嘴塗佈法、噴墨法、網版印刷法、凹版印刷法、橡膠版輪轉印刷法等公知方法。就從較簡便且容易獲得表面平坦性的觀點，較佳係旋塗法、模頭塗佈法、浸塗法。 The coating composition is applied to a suitable substrate such as glass or plastic, and a cured film, that is, a porous film or a light-scattering film can be formed by removing the solvent. The coating method can be, for example, spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, nozzle coating, spraying A known method such as an ink method, a screen printing method, a gravure printing method, or a rubber plate rotary printing method. From the viewpoint of being relatively simple and easy to obtain surface flatness, a spin coating method, a die coating method, and a dip coating method are preferred.

溶劑之除去係可利用加熱乾燥、減壓乾燥等實施。施行乾燥之際，、乾燥溫度的上限較佳係未滿400℃。若未滿400℃，便可抑制聚矽烷化合物分解。又，乾燥溫度的下限值係只要能去除所使用溶劑之程度的溫度(即溶劑沸點以上)便可。施行乾燥之際，可在大氣中施行乾燥、亦可在惰性氣體環境下施行乾燥。 The removal of the solvent can be carried out by heat drying, drying under reduced pressure, or the like. When drying is performed, the upper limit of the drying temperature is preferably less than 400 °C. If it is less than 400 ° C, the decomposition of the polydecane compound can be suppressed. Further, the lower limit of the drying temperature may be any temperature (i.e., the boiling point of the solvent) at which the solvent to be used can be removed. When drying is carried out, it can be dried in the atmosphere or dried in an inert gas atmosphere.

III.多孔質膜 III. Porous membrane

依如上述所形成的硬化物係如後述有形成空隙的多孔質膜。此種膜係除能有效使用為後述光散射膜之外，例如尚可利用多孔質膜現象而使用為吸附體、或使用為觸媒等機能性物質的載持體等等。 The cured product formed as described above has a porous film in which voids are formed as will be described later. In addition to the light-scattering film which will be described later, such a film system can be used as an adsorbent or a carrier which is a functional substance such as a catalyst, for example, by using a porous film phenomenon.

IV.光散射膜 IV. Light scattering film

依如上述所形成的硬化物係如後述有形成空隙的多孔質膜。空隙的平均直徑係100nm以上，因而硬化物具有散射特性，可利用為光散 射膜。例如有效使用為有機電場發光元件的光取出膜。 The cured product formed as described above has a porous film in which voids are formed as will be described later. The average diameter of the voids is 100 nm or more, and thus the cured product has scattering characteristics and can be utilized as light scattering. Film. For example, a light extraction film that is an organic electric field light-emitting element is effectively used.

<相關折射率> <Related refractive index>

圖5所示係有機電場發光元件100之一例。由發光層3所發光的光係全量通過折射率較高於發光層3的陽極(ITO)6，並到達ITO6與散射膜7的界面處。此時，當散射膜7的折射率係與發光層3的折射率同等、或更高的情況，發光光在界面處不會被反射而會全量射入散射膜7中，便可獲得最高的光取出效率。 An example of the organic electroluminescence element 100 is shown in FIG. The light emitted by the light-emitting layer 3 passes through the anode (ITO) 6 having a higher refractive index than the light-emitting layer 3 and reaches the interface between the ITO 6 and the scattering film 7. At this time, when the refractive index of the scattering film 7 is equal to or higher than the refractive index of the light-emitting layer 3, the light-emitting light is not reflected at the interface and is totally incident into the scattering film 7, so that the highest is obtained. Light extraction efficiency.

所以，散射膜的折射率較佳係與發光層的折射率同等、或更高。一般發光層材料的折射率係1.7~1.8範圍(例：參(8-羥基喹啉)鋁：Alq₃的折射率=1.72@550nm)，因而散射膜的折射率較佳係1.8以上、更佳係1.9以上。此處，構成本發明塗佈用組成物的聚矽烷化合物之折射率係1.7以上，且金屬氧化物(例如氧化鋅)的折射率係2.0，因而可當作具備有如上述較佳折射率的散射膜並組裝於元件中。 Therefore, the refractive index of the scattering film is preferably equal to or higher than the refractive index of the light-emitting layer. Generally, the refractive index of the luminescent layer material is in the range of 1.7 to 1.8 (for example, ginseng (8-hydroxyquinoline) aluminum: refractive index of Alq ₃ = 1.72@550 nm), and thus the refractive index of the scattering film is preferably 1.8 or more, more preferably Is 1.9 or more. Here, the polydecane compound constituting the coating composition of the present invention has a refractive index of 1.7 or more, and the metal oxide (for example, zinc oxide) has a refractive index of 2.0, and thus can be regarded as having a scattering having a preferred refractive index as described above. The film is assembled into the component.

再者，圖6所示係在玻璃基板等基板8的光射出面側有形成散射膜7的有機電場發光元件100一例。在玻璃基板8的光射出面側設有散射膜7的有機電場發光元件100，係可抑制玻璃基板8與大氣間之界面處所生成發光光的取出損失。此時，當散射膜7的折射率係與玻璃基板8的折射率(約1.5)同等、或更高的情況，發光光在界面處不會被反射而是全量射入散射膜中，便可獲得光取出效率。 In addition, an example of the organic electroluminescence element 100 in which the scattering film 7 is formed on the light-emitting surface side of the substrate 8 such as a glass substrate is shown in FIG. The organic electroluminescence element 100 in which the scattering film 7 is provided on the light-emitting surface side of the glass substrate 8 can suppress the extraction loss of the luminescent light generated at the interface between the glass substrate 8 and the atmosphere. At this time, when the refractive index of the scattering film 7 is equal to or higher than the refractive index (about 1.5) of the glass substrate 8, the luminescent light is not reflected at the interface but is totally incident into the scattering film. Obtain light extraction efficiency.

<相關空隙> <related gap>

由本發明的塗佈用組成物所獲得光散射膜，係具有在表面與內部 均有形成空隙的結構。相關空隙的平均直徑係10~800nm。就從具有更佳散射特性的觀點，空隙的平均直徑較佳係100~600nm。再者，相關空隙的面積率較佳係2~40%。若在此範圍內，即便形成膜仍可維持物理性強度，例如有機電場發光元件之製造步驟中，可避免在步驟途中遭受破損。又，保存安定性亦優異。 The light-scattering film obtained from the coating composition of the present invention has a surface and an interior There are structures that form voids. The average diameter of the associated voids is 10 to 800 nm. From the viewpoint of having better scattering characteristics, the average diameter of the voids is preferably from 100 to 600 nm. Furthermore, the area ratio of the relevant voids is preferably 2 to 40%. Within this range, the physical strength can be maintained even if the film is formed. For example, in the manufacturing step of the organic electric field light-emitting element, damage during the step can be avoided. Moreover, the preservation stability is also excellent.

本發明的光散射膜，空隙(即有填充空氣的空間)將發揮散射體的機能。藉由空氣(折射率=1.0)、及金屬氧化物粒子與聚矽烷化合物的混合物間之較大折射率差，便可獲得高霧度(即高散射特性)。會形成空隙的機構雖尚未明朗，但可推測在所塗佈溶劑進行乾燥的過程中，金屬氧化物粒子與聚矽烷化合物的混合物會在內含氣泡之情況下，一邊與溶劑相分離一邊凝聚、結合而形成空隙。所以，空隙的平均直徑、空隙的體積率等，係利用當作組成物使用的聚矽烷化合物之分子量、金屬氧化物的平均直徑、聚矽烷化合物與金屬氧化物的混合比、胺基甲酸酯化合物的種類與存在比等便可進行控制。 In the light-scattering film of the present invention, voids (i.e., spaces filled with air) function as scatterers. High haze (i.e., high scattering characteristics) can be obtained by air (refractive index = 1.0) and a large refractive index difference between a mixture of metal oxide particles and a polydecane compound. Although the mechanism for forming a void is not clear, it is presumed that during the drying of the applied solvent, the mixture of the metal oxide particles and the polydecane compound is agglomerated while being separated from the solvent while containing bubbles therein. The voids are formed by bonding. Therefore, the average diameter of the voids, the volume fraction of the voids, and the like are the molecular weight of the polydecane compound used as the composition, the average diameter of the metal oxide, the mixing ratio of the polydecane compound to the metal oxide, and the urethane. The type and ratio of the compounds can be controlled.

再者，因為散射體有空隙，因而藉由與空氣進行取代便可填充任意的化學物種。例如在形成該散射膜之後，重疊塗佈任意溶液或分散液的方法，或者利用含浸的方法便可在空隙中填充任意化學物種。再者，藉由將空隙取代為任意具有折射率的化學物種，便可調整散射特性、或與螢光體等發色化學物種取代。藉此，便可調整發色特性俾供應用。又，利用屬於孔質膜的現象，亦可利用為吸附體、或利用為觸媒等機能性物質的載持體。 Furthermore, since the scatterer has voids, any chemical species can be filled by substitution with air. For example, after the formation of the scattering film, any solution or dispersion may be applied by overlapping, or any chemical species may be filled in the void by the method of impregnation. Furthermore, by replacing the voids with any chemical species having a refractive index, the scattering properties can be adjusted or replaced with chromogenic chemical species such as phosphors. By this, the coloring characteristics can be adjusted and supplied. Further, the phenomenon of belonging to the pore membrane may be used as a carrier or a carrier which is a functional substance such as a catalyst.

再者，在該散射膜上亦可形成任意的被覆層。例如當 將散射膜利用為有機電場發光元件的光取出膜時，會有要求最表面的平滑性、耐溶劑性、耐酸、耐鹼性等之情況。在彌補對該散射膜所要求特性之目的下會有形成被覆層。該被覆層的折射率係為抑制在界面處的發光光反射，最好與該散射膜同等或較高。 Further, an arbitrary coating layer may be formed on the scattering film. For example when When the scattering film is used as a light extraction film of an organic electric field light-emitting element, the smoothness, solvent resistance, acid resistance, alkali resistance, and the like of the outermost surface may be required. A coating layer is formed for the purpose of compensating for the characteristics required for the scattering film. The refractive index of the coating layer is such that the reflection of the luminescent light at the interface is suppressed, and it is preferably equal to or higher than the scattering film.

以下，針對含有本發明散射膜的有機電場發光元件、有機EL顯示裝置及有機EL照明裝置之實施態樣，參照圖5進行詳細說明，惟本發明在不逾越主旨之前提下，並不僅侷限於該等內容。另外，本發明的塗佈用組成物係如圖5所示，藉由塗佈於基板8上而層狀形成散射膜7，且配置於基板8與陽極6之間。 Hereinafter, an embodiment of an organic electroluminescence device, an organic EL display device, and an organic EL illumination device including the scattering film of the present invention will be described in detail with reference to FIG. 5. However, the present invention is not limited to the prior art and is not limited to The content. Further, as shown in FIG. 5, the coating composition of the present invention is formed by layering the scattering film 7 on the substrate 8, and is disposed between the substrate 8 and the anode 6.

V.有機電場發光元件 V. Organic electric field light-emitting element (基板) (substrate)

基板8係成為有機電場發光元件100的支撐體，通常係使用石英、玻璃的板、金屬板或金屬箔、塑膠薄膜或薄片等。該等之中，較佳係玻璃板、或例如聚酯、聚甲基丙烯酸酯、聚碳酸酯、聚碸、聚醯亞胺等透明合成樹脂的板或薄膜。基板8係就從不易引發因外氣而造成有機電場發光元件劣化的觀點，較佳係高阻氣性材質。所以，特別係當使用如合成樹脂製基板等之類的低阻氣性材質時，最好在基板8的至少單面上設置緻密矽氧化膜等俾提升阻氣性。 The substrate 8 serves as a support for the organic electroluminescent device 100, and generally, a plate made of quartz or glass, a metal plate or a metal foil, a plastic film or a sheet, or the like is used. Among these, a glass plate or a plate or film of a transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, polyfluorene or polyimine is preferred. The substrate 8 is preferably a high gas barrier material from the viewpoint that it is less likely to cause deterioration of the organic electric field light-emitting element due to external air. Therefore, in particular, when a low gas barrier material such as a synthetic resin substrate or the like is used, it is preferable to provide a dense tantalum oxide film or the like on at least one surface of the substrate 8 to improve gas barrier properties.

(陽極) (anode)

陽極6係負責對發光層3側的層注入電洞之機能。陽極6通常係由：鋁、金、銀、鎳、鈀、白金等金屬；銦及/或錫的氧化物等金屬氧 化物；碘化銅等鹵化金屬；碳黑及聚(3-甲基噻吩)、聚吡咯、聚苯胺等導電性高分子等等構成。陽極6之形成通常大多採行濺鍍法、真空蒸鍍法等乾式法實施。又，當使用銀等金屬微粒子、碘化銅等微粒子、碳黑、導電性金屬氧化物微粒子、導電性高分子微粉末等形成陽極時，亦可藉由使分散於適當的黏結劑樹脂溶液中，再塗佈基板8上而形成。又，當陽極6係由導電性高分子構成的情況，亦可利用電解聚合直接在基板上形成薄膜，或者在基板上塗佈導電性高分子而形成陽極(APP1.Phys.Lett.，第60卷，第2711頁，1992年)。 The anode 6 is responsible for the function of injecting holes into the layer on the side of the light-emitting layer 3. The anode 6 is usually made of a metal such as aluminum, gold, silver, nickel, palladium or platinum; metal oxide such as an oxide of indium and/or tin. a halogenated metal such as copper iodide; a conductive polymer such as carbon black or poly(3-methylthiophene), polypyrrole or polyaniline; The formation of the anode 6 is usually carried out by a dry method such as a sputtering method or a vacuum deposition method. In addition, when an anode is formed using fine particles such as silver fine particles such as silver or copper iodide, carbon black, conductive metal oxide fine particles, or conductive polymer fine powder, it may be dispersed in a suitable binder resin solution. And formed by coating the substrate 8. Further, when the anode 6 is made of a conductive polymer, a thin film may be directly formed on the substrate by electrolytic polymerization, or a conductive polymer may be applied onto the substrate to form an anode (APP1. Phys. Lett., 60th) Vol. 2711, 1992).

陽極6通常係屬於單層結構，亦可適當地為積層結構。當陽極6係積層結構的情況，亦可在第1層的陽極上積層的不同的導電材料。陽極6的厚度係只要配合必要的透明性與材質等再行決定便可。特別係當需要高透明性的情況，較佳係可見光穿透率成為60%以上的厚度、更佳係成為80%以上的厚度。陽極6的厚度通常係5nm以上、較佳係10nm以上，又通常係1000nm以下、較佳係500nm以下。另一方面，當不需要透明性的情況，陽極6的厚度只要配合必要強度等再任意設定厚度便可，此情況，陽極亦可與基板相同厚度。 The anode 6 is usually of a single layer structure, and may suitably have a laminate structure. In the case where the anode 6 is a laminated structure, a different conductive material may be laminated on the anode of the first layer. The thickness of the anode 6 can be determined by matching the necessary transparency and material. In particular, when high transparency is required, the visible light transmittance is preferably 60% or more, and more preferably 80% or more. The thickness of the anode 6 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 6 may be arbitrarily set to a thickness in accordance with the required strength, and in this case, the anode may have the same thickness as the substrate.

當在陽極6的表面施行成膜時，在成膜前藉由施行紫外線+臭氧、氧電漿、氬電漿等處理，便可去除陽極上的雜質，且調整離子化電位，俾提升電洞注入性，故屬較佳。 When the film is formed on the surface of the anode 6, by performing ultraviolet light + ozone, oxygen plasma, argon plasma or the like before film formation, impurities on the anode can be removed, and the ionization potential can be adjusted, and the hole can be raised. Injectability is preferred.

(電洞注入層) (hole injection layer)

負責從陽極6側朝發光層3側輸送電洞之機能的層，通常稱為「電 洞注入輸送層」或「電洞輸送層」。然後，當負責從陽極6側朝發光層3側輸送電洞之機能的層係達2層以上之情況，便將較靠近陽極側的層稱為「電洞注入層1」。電洞注入層1係就強化從陽極6朝發光層6側輸送電洞之機能的觀點，最好使用。當有使用電洞注入層1時，通常電洞注入層1係形成於陽極6上。 The layer responsible for the function of transporting holes from the side of the anode 6 toward the side of the light-emitting layer 3, which is usually called "electricity" Hole injection layer" or "hole transport layer". Then, when the layer responsible for transporting the hole from the anode 6 side toward the light-emitting layer 3 side has two or more layers, the layer closer to the anode side is referred to as "hole injection layer 1". The hole injection layer 1 is preferably used in view of enhancing the function of transporting holes from the anode 6 toward the light-emitting layer 6 side. When the hole injection layer 1 is used, the hole injection layer 1 is usually formed on the anode 6.

電洞注入層1之膜厚通常係1nm以上、較佳係5nm以上，且通常係1000nm以下、較佳係500nm以下。電洞注入層1之形成方法係可為真空蒸鍍法、亦可為濕式成膜法。就從成膜性優異的觀點，最好利用濕式成膜法形成。電洞注入層1較佳係含有電洞輸送性化合物、更佳係含有電洞輸送性化合物與電子受體性化合物。又，在電洞注入層中較佳係含有陽離子自由基化合物、更佳係含有陽離子自由基化合物與電洞輸送性化合物。 The film thickness of the hole injection layer 1 is usually 1 nm or more, preferably 5 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. The method of forming the hole injection layer 1 may be a vacuum deposition method or a wet film formation method. From the viewpoint of excellent film formability, it is preferably formed by a wet film formation method. The hole injection layer 1 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Further, it is preferable that the hole injection layer contains a cationic radical compound, more preferably a cationic radical compound and a hole transporting compound.

(電洞輸送性化合物) (hole transporting compound)

電洞注入層形成用組成物通常係含有會成為電洞注入層1的電洞輸送性化合物。又，濕式成膜法的情況，通常亦更進一步含有溶劑。電洞注入層形成用組成物較佳係電洞輸送性高、能效率佳輸送所注入電洞者。所以，較佳係電洞移動率較大、在製造時或使用時等不易產生成為陷阱的雜質者。又，最好係安定性優異、離子化電位小、對可見光的透明性高。特別係當電洞注入層1鄰接發光層3時，最好不會將來自發光層的發光予以消光者、或不會與發光層形成激態錯合物而導致發光效率降低者。 The composition for forming a hole injection layer usually contains a hole transporting compound which will become the hole injection layer 1. Further, in the case of the wet film formation method, a solvent is usually further contained. The composition for forming a hole injection layer is preferably one in which the hole is highly transportable and the energy can be efficiently transported into the hole. Therefore, it is preferable that the hole mobility rate is large, and it is difficult to generate impurities which are traps at the time of manufacture or use. Further, it is preferable that the stability is excellent, the ionization potential is small, and the transparency to visible light is high. In particular, when the hole injection layer 1 is adjacent to the light-emitting layer 3, it is preferable that the light emitted from the light-emitting layer is not dull or does not form an excimer with the light-emitting layer, resulting in a decrease in luminous efficiency.

電洞輸送性化合物就從陽極6朝電洞注入層1的電荷注入障壁觀點，較佳係具有4.5eV~6.0eV離子化電位的化合物。電洞輸送性化合物例係可舉例如：芳香族胺系化合物、酞菁系化合物、卟啉系化合物、寡噻吩系化合物、聚噻吩系化合物、苄基苯系化合物、利用茀基連結三級胺的化合物、腙系化合物、矽氮烷系化合物系化合物、喹吖酮系化合物等。 The hole transporting compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of the charge injection barrier of the anode 6 toward the hole injection layer 1. Examples of the hole transporting compound include an aromatic amine compound, a phthalocyanine compound, a porphyrin compound, an oligothiophene compound, a polythiophene compound, a benzylbenzene compound, and a tertiary amine bonded via a mercapto group. A compound, an anthraquinone compound, a decazane compound compound, a quinophthalone compound, or the like.

上述所例示化合物中，就從非晶質性與可見光穿透性的觀點，較佳係芳香族胺化合物、更佳係芳香族三級胺化合物。此處，所謂「芳香族三級胺化合物」係具有芳香族三級胺結構的化合物，亦涵蓋具有源自芳香族三級胺之基的化合物。芳香族三級胺化合物的種類並無特別的限制，就從較容易利用表面平滑化效果而獲得均勻發光的觀點，較佳係使用重量平均分子量1000以上且1000000以下的高分子化合物(重複單元相連接的聚合型化合物)。芳香族三級胺高分子化合物的較佳例係可例如具有下式(1)所示重複單元的高分子化合物等： Among the above-exemplified compounds, an aromatic amine compound and a more preferred aromatic tertiary amine compound are preferred from the viewpoint of amorphousness and visible light transmittance. Here, the "aromatic tertiary amine compound" is a compound having an aromatic tertiary amine structure, and also includes a compound having a group derived from an aromatic tertiary amine. The type of the aromatic tertiary amine compound is not particularly limited, and from the viewpoint of obtaining uniform light emission by the surface smoothing effect, it is preferred to use a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (repeating unit phase). Connected polymeric compound). A preferred example of the aromatic tertiary amine polymer compound is, for example, a polymer compound having a repeating unit represented by the following formula (1):

(式(1)中，Ar¹與Ar²係表示各自獨立的亦可具有取代基之芳香族烴基、或亦可具有取代基之芳香族雜環基。Ar³~Ar⁵係表示各自獨立的亦可具有取代基之芳香族烴基、或亦可具有取代基之芳香族雜環基。Y係表示從述連接基群中選擇的連接基。又，Ar¹~Ar⁵中，在 同一N原子上所鍵結的二個基亦可相互鍵結形成環。 (In the formula (1), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ³ to Ar ⁵ represent independent Further, it may have an aromatic hydrocarbon group having a substituent or an aromatic heterocyclic group which may have a substituent. Y represents a linking group selected from the group of the linking groups. Further, in Ar ¹ to Ar ⁵ , the same N atom The two groups bonded to each other may also be bonded to each other to form a ring.

(上述各式中，Ar⁶~Ar¹⁶係表示各自獨立的亦可具有取代基之芳香族烴基、或亦可具有取代基之芳香族雜環基。R¹及R²係表示各自獨立的氫原子或任意取代基。)Ar¹~Ar¹⁶的芳香族烴基及芳香族雜環基，就從高分子化合物的溶解性、耐熱性、電洞注入輸送性之觀點，較佳係源自苯環、萘環、菲環、噻吩環、吡啶環的基，更佳係源自苯環、萘環的基。 (In the above formulae, Ar ⁶ to Ar ¹⁶ each represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. R ¹ and R ² each represent a hydrogen independently. The atomic or arbitrary substituent.) The aromatic hydrocarbon group and the aromatic heterocyclic group of Ar ¹ to Ar ¹⁶ are preferably derived from a benzene ring from the viewpoints of solubility, heat resistance and hole injection transportability of the polymer compound. The group of a naphthalene ring, a phenanthrene ring, a thiophene ring or a pyridine ring is more preferably a group derived from a benzene ring or a naphthalene ring.

具有式(1)所示重複單元的芳香族三級胺高分子化合物具體例，係可例如國際公開第2005/089024號所記載者等。 Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (1) are, for example, those described in International Publication No. 2005/089024.

(電子受體性化合物) (electron acceptor compound)

在電洞注入層1中，因為利用電洞輸送性化合物的氧化，便可提升電洞注入層的導電率，因而較佳係含有電子受體性化合物。 In the hole injection layer 1, since the conductivity of the hole injection layer can be improved by oxidation of the hole transporting compound, it is preferable to contain an electron acceptor compound.

電子受體性化合物較佳係具有氧化力、且具有從上述電洞輸送性化合物中接受一電子之能力的化合物，具體而言，較佳係電子親和力達4eV以上的化合物、更佳係電子親和力達5eV以上的化合 物。此種電子受體性化合物係可例如從三芳基硼化合物、鹵化金屬、路易斯酸、有機酸、鎓鹽、芳基胺與鹵化金屬的鹽、芳基胺與路易斯酸的鹽所構成群組中選擇1種或2種以上的化合物等。具體係可舉例如：4-異丙基-4'-甲基二苯基碘鎓四(五氟苯基)硼酸鹽、三苯基四氟硼酸鋶等經有機基取代的鎓鹽(國際公開2005/089024號)；氯化鐵(III)(日本專利特開平11-251067號公報)、過氧二硫酸銨等高原子價的無機化合物；四氰基乙烯等氰化合物；三(五氟苯基)硼烷(日本專利特開2003-31365號公報)等芳香族硼化合物；富勒烯衍生物及碘等。 The electron acceptor compound is preferably a compound having an oxidizing power and having an ability to receive an electron from the above hole transporting compound, and specifically, a compound having an electron affinity of 4 eV or more, and a better electron affinity. Up to 5eV or more Things. Such an electron acceptor compound can be, for example, a group consisting of a triarylboron compound, a metal halide, a Lewis acid, an organic acid, a phosphonium salt, a salt of an arylamine and a metal halide, a salt of an arylamine and a Lewis acid. One or two or more compounds are selected. Specifically, for example, an organic group-substituted sulfonium salt such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate or lanthanum triphenyltetrafluoroborate (International Publication) 2005/089024); iron (III) chloride (Japanese Patent Laid-Open No. Hei 11-251067), high-valent inorganic compounds such as ammonium peroxydisulfate; cyano compounds such as tetracyanoethylene; and tris(pentafluorobenzene) An aromatic boron compound such as a borane (Japanese Patent Laid-Open Publication No. 2003-31365); a fullerene derivative, iodine, or the like.

(陽離子自由基化合物) (cationic radical compound)

陽離子自由基化合物較佳係由屬於從電洞輸送性化合物去除一電子之化學物種的陽離子自由基、與由共軛陰離子所構成的離子化合物。但，當陽離子自由基係源自電洞輸送性高分子化合物時，陽離子自由基便成為從高分子化合物的重複單元中去除一電子的結構。 The cationic radical compound is preferably a cation radical composed of a chemical species which removes one electron from the hole transporting compound and an ionic compound composed of a conjugated anion. However, when the cationic radical is derived from the hole transporting polymer compound, the cationic radical is a structure in which one electron is removed from the repeating unit of the polymer compound.

陽離子自由基較佳係從當作電洞輸送性化合物用的前述化合物中去除一電子的化學物種。就從非晶質性、可見光穿透率、耐熱性、及溶解性等觀點，最好係從電洞輸送性化合物的較佳化合物中去除一電子之化學物種。此處，陽離子自由基化合物係藉由前述電洞輸送性化合物與電子受體性化合物相混合便可生成。即，藉由前述電洞輸送性化合物與電子受體性化合物相混合，便會引發從電洞輸送性化合物朝電子受體性化合物的電子移動，而生成由電洞輸送性化合物的陽離子自由基與共軛陰離子構成之陽離子化合物。 The cationic radical is preferably a chemical species from which an electron is removed from the aforementioned compound used as a hole transporting compound. From the viewpoints of amorphousness, visible light transmittance, heat resistance, solubility, and the like, it is preferred to remove an electron chemical species from a preferred compound of the hole transporting compound. Here, the cationic radical compound is produced by mixing the above-mentioned hole transporting compound and an electron accepting compound. In other words, when the hole transporting compound and the electron accepting compound are mixed, electron transfer from the hole transporting compound to the electron accepting compound is caused to generate a cationic radical derived from the hole transporting compound. a cationic compound composed of a conjugated anion.

PEDOT/PSS(Adv.Mater.,2000年，第12卷，第481頁)、苯胺綠鹽酸鹽(J.Phys.Chem.,1990年，第94卷，第7716頁)等源自高分子化合物的陽離子自由基化合物，利用氧化聚合(脫氫聚合)亦可生成。此處所謂的「氧化聚合」係指使單體在酸性溶液中、或使用過氧二硫酸鹽等施行化學性或電化學性氧化者。該氧化聚合(脫氫聚合)的情況，單體會因氧化而高分子化，且會生成源自酸性溶液的陰離子形成共軛陰離子之從高分子的重複單元中去除一電子的陽離子自由基。 PEDOT/PSS (Adv. Mater., 2000, Vol. 12, p. 481), aniline green hydrochloride (J. Phys. Chem., 1990, Vol. 94, p. 7716), etc. derived from polymers The cationic radical compound of the compound can also be produced by oxidative polymerization (dehydropolymerization). The term "oxidative polymerization" as used herein means a chemical or electrochemical oxidation of a monomer in an acidic solution or using peroxodisulfate. In the case of the oxidative polymerization (dehydrogenation polymerization), the monomer is polymerized by oxidation, and an anion derived from an acidic solution forms a conjugated anion, and a cation radical of one electron is removed from the repeating unit of the polymer.

<依照濕式成膜法施行的電洞注入層形成> <Formation of hole injection layer according to wet film formation method>

當利用濕式成膜法形成電洞注入層時，通常係與能溶解電洞注入層材料的溶劑(電洞注入層用溶劑)相混合，而製備為成膜用組成物(電洞注入層形成用組成物)，將該電洞注入層形成用組成物塗佈於屬於電洞注入層下層的層(通常係陽極)上而成膜，經乾燥便可形成。 When the hole injection layer is formed by the wet film formation method, it is usually mixed with a solvent capable of dissolving the material of the hole injection layer (solvent for the hole injection layer) to prepare a film formation composition (hole injection layer). The composition for forming a layer is formed by applying the composition for forming a hole injection layer to a layer (usually an anode) which is a lower layer of the hole injection layer, and is formed by drying.

電洞注入層形成用組成物中的電洞輸送性化合物濃度，係在不致明顯損及本發明效果之前提下可為任意，就從膜厚均勻性的觀點，越低越佳，又另一方面，就從電洞注入層不易生成缺陷的觀點，越高越佳。具體而言，較佳係0.01重量%以上、更佳係0.1重量%以上、特佳係0.5重量%以上，又另一方面，較佳係70重量%以下、更佳係60重量%以下、特佳係50重量%以下。 The concentration of the hole transporting compound in the composition for forming a hole injection layer can be arbitrarily removed without significantly impairing the effects of the present invention, and from the viewpoint of film thickness uniformity, the lower the better, the other On the other hand, from the viewpoint that the hole injection layer is less likely to generate defects, the higher the better. Specifically, it is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and particularly preferably 0.5% by weight or more, and on the other hand, preferably 70% by weight or less, more preferably 60% by weight or less, and particularly preferably 60% by weight or less. Preferably, it is 50% by weight or less.

溶劑係可例如：醚系溶劑、酯系溶劑、芳香族烴系溶劑、醯胺系溶劑等。醚系溶劑係可例如：乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚醋酸酯(PGMEA)等脂肪族醚；以及1,2-二甲氧基苯、 1,3-二甲氧基苯、茴香醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基茴香醚、2,4-二甲基茴香醚等芳香族醚等等。 The solvent may be, for example, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent or a guanamine solvent. The ether solvent may, for example, be an aliphatic ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate (PGMEA); and 1,2-dimethoxybenzene. 1,3-Dimethoxybenzene, anisole, phenylethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4 An aromatic ether such as dimethyl anisole or the like.

酯系溶劑係可例如：醋酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯等等。芳香族烴系溶劑係可例如：甲苯、二甲苯、環己苯、3-異丙基聯苯、1,2,3,4-四甲基苯、1,4-二異丙基苯、環己苯、甲基萘等。醯胺系溶劑係可例如：N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等。 The ester solvent may, for example, be an aromatic ester such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate or n-butyl benzoate. The aromatic hydrocarbon solvent may be, for example, toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene or a ring. Hexabenzene, methylnaphthalene, and the like. The guanamine solvent may be, for example, N,N-dimethylformamide or N,N-dimethylacetamide.

該等之外，尚可使用二甲亞碸等。電洞注入層1利用濕式成膜法的形成，通常係在製備電洞注入層形成用組成物後，將其塗佈成膜於屬於電洞注入層1下層的層(通常係陽極6)上，經乾燥而實施。電洞注入層1通常係在成膜後，經加熱、減壓乾燥等而使塗佈膜乾燥。 In addition to these, it is also possible to use dimethyl hydrazine or the like. The hole injection layer 1 is formed by a wet film formation method, and is usually applied to a layer for forming a hole injection layer, and then applied to a layer belonging to the lower layer of the hole injection layer 1 (usually an anode 6). It is carried out by drying. The hole injection layer 1 is usually dried after being formed into a film, heated, dried under reduced pressure, or the like.

<利用真空蒸鍍法進行的電洞注入層形成> <Formation of hole injection layer by vacuum evaporation method>

當利用真空蒸鍍法形成電洞注入層1時，通常將電洞注入層1的構成材料(前述電洞輸送性化合物、電子受體性化合物等)1種或2種以上，裝入真空容器內所設置的坩堝中(使用2種以上的材料時，通常係分別裝入各自的坩堝中)，將真空容器內利用真空泵施行排氣至10^-4Pa左右之後，加熱坩堝(使用2種以上的材料時，通常係加熱各個坩堝)，一邊控制坩堝內的材料蒸發量，一邊使其蒸發(使用2種以上的材料時，通常係各自獨立地一邊控制蒸發量一邊使蒸發)，便在相對向於坩堝放置的基板上之陽極上形成電洞注入層。另外，使用2種以上的材 料時，亦可將該等混合物放入坩堝中，經加熱使蒸發而形成電洞注入層。 When the hole injection layer 1 is formed by a vacuum deposition method, one or two or more kinds of the constituent materials (the above-mentioned hole transporting compound, electron acceptor compound, etc.) of the hole injection layer 1 are usually placed in a vacuum container. In the sputum provided in the inside (when two or more materials are used, they are usually placed in the respective sputum), and the inside of the vacuum vessel is evacuated to about 10 ^-4 Pa by a vacuum pump, and then heated (using two or more types) When the material is used, it is usually heated to control the amount of evaporation of the material in the crucible, and when it is used, when two or more materials are used, it is usually controlled to control evaporation while independently evaporating. A hole injection layer is formed on the anode on the substrate on which the crucible is placed. Further, when two or more kinds of materials are used, the mixture may be placed in a crucible, and heated to evaporate to form a hole injection layer.

蒸鍍時的真空度係在不致明顯損及本發明效果之前提下，其餘並無限定，通常係0.1×10^-6Torr(0.13×10^-4Pa)以上、且9.0×10^-6Torr(12.0×10^-4Pa)以下。蒸鍍速度係在不致明顯損及本發明效果之前提下，其餘並無限定，通常係0.1A/秒以上、且5.0A/秒以下。蒸鍍時的成膜溫度係在不致明顯損及本發明效果之前提下，其餘並無限定，較佳係依10℃以上且50℃以下實施。另外，電洞注入層1亦可與後述電洞輸送層同樣地進行交聯。 The degree of vacuum at the time of vapor deposition is not limited until the effect of the present invention is not significantly impaired, and the rest is not limited, and is usually 0.1 × 10 ^-6 Torr (0.13 × 10 ^-4 Pa) or more and 9.0 × 10 ^-6 Torr ( 12.0 × 10 ^-4 Pa) or less. The vapor deposition rate is not limited until the effect of the present invention is significantly impaired, and the rest is not limited, and is usually 0.1 A/sec or more and 5.0 A/sec or less. The film formation temperature at the time of vapor deposition is not limited until the effect of the present invention is significantly impaired, and the rest is not limited, and it is preferably carried out at 10 ° C or more and 50 ° C or less. Further, the hole injection layer 1 may be crosslinked in the same manner as the hole transport layer described later.

(電洞輸送層) (hole transport layer)

電洞輸送層2係負責從陽極6側朝發光層3側輸送電洞機能的層。電洞輸送層2在本發明的有機電場發光元件100中並非屬於必要的層，但就從強化陽極6朝發光層3輸送電洞之機能的觀點，最好使用該層。使用電洞輸送層2時，通常電洞輸送層2係形成於陽極6與發光層3之間。又，當設有上述電洞注入層1時，便形成於電洞注入層1與發光層3之間。 The hole transport layer 2 is responsible for transporting the layer of the hole function from the anode 6 side toward the light-emitting layer 3 side. The hole transport layer 2 is not an essential layer in the organic electroluminescent device 100 of the present invention, but it is preferable to use the layer from the viewpoint of the function of transporting the hole from the reinforcing anode 6 to the light-emitting layer 3. When the hole transport layer 2 is used, the hole transport layer 2 is usually formed between the anode 6 and the light-emitting layer 3. Further, when the hole injection layer 1 is provided, it is formed between the hole injection layer 1 and the light-emitting layer 3.

電洞輸送層2的膜厚通常係5nm以上、較佳係10nm以上，又另一方面，通常係300nm以下、較佳係100nm以下。電洞輸送層2之形成方法係可為真空蒸鍍法、亦可為濕式成膜法。就從成膜性優異的觀點，較佳係利用濕式成膜法形成。 The film thickness of the hole transport layer 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less. The method of forming the hole transport layer 2 may be a vacuum deposition method or a wet film formation method. From the viewpoint of excellent film formability, it is preferably formed by a wet film formation method.

電洞輸送層2通常係含有將成為電洞輸送層的電洞輸送 性化合物。電洞輸送層中所含有的電洞輸送性化合物，特別係可例如：4,4'-雙[N-(1-萘基)-N-苯基胺基]聯苯所代表，由含有2個以上三級胺的2個以上縮合芳香族環，取代氮原子的芳香族二胺(日本專利特開平5-234681號公報)；4,4',4"-三(1-萘基苯基胺基)三苯胺等具有星爆式結構的芳香族胺化合物(J.Lumin.，第72-74卷、第985頁、1997年)；由三苯胺的四聚體所構成之芳香族胺化合物(Chem.Commun.，第2175頁、1996年)；2,2',7,7'-四(二苯基胺基)-9,9'-螺雙茀等螺化合物(Synth.Metals，第91卷、第209頁、1997年)；4,4'-N,N'-二咔唑聯苯等咔唑衍生物等等。又，較佳係使用例如聚乙烯咔唑、聚乙烯三苯胺(日本專利特開平7-53953號公報)、含有四苯基聯苯胺的聚伸芳基醚碸(Polym.Adv.Tech.，第7卷、第33頁、1996年)等。 The hole transport layer 2 usually contains a hole transport that will become a hole transport layer. Sex compounds. The hole transporting compound contained in the hole transporting layer may be, for example, represented by 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, which contains 2 Two or more condensed aromatic rings of one or more tertiary amines, and aromatic diamines substituted with nitrogen atoms (Japanese Patent Laid-Open No. Hei 5-234681); 4,4',4"-tris(1-naphthylphenyl) Aromatic amine compounds having a starburst structure such as amino)triphenylamine (J. Lumin., vol. 72-74, p. 985, 1997); aromatic amine compounds composed of tetramers of triphenylamine (Chem. Commun., p. 2175, 1996); 2,2',7,7'-tetrakis(diphenylamino)-9,9'-spirobipurine and other spiro compounds (Synth.Metals, p. 91, 209, 1997); oxazole derivatives such as 4,4'-N, N'-dicarbazole biphenyl, etc. Further, it is preferred to use, for example, polyvinyl carbazole or polyethylene triphenylamine. (Japanese Patent Laid-Open No. Hei 7-53953), poly(arylene ether) containing tetraphenylbenzidine (Polym. Adv. Tech., Vol. 7, p. 33, 1996).

<利用濕式成膜法進行的電洞輸送層之形成> <Formation of a hole transport layer by a wet film formation method>

當利用濕式成膜法形成電洞輸送層2時，通常係與上述利用濕式成膜法形成電洞注入層1的情況同樣的，只是取代電洞注入層形成用組成物，改為使用電洞輸送層形成用組成物便可形成。當利用濕式成膜法形成電洞輸送層2時，通常電洞輸送層形成用組成物係更進一步含有溶劑。電洞輸送層形成用組成物中所使用的溶劑，係可使用與上述電洞注入層形成用組成物所使用溶劑為同樣的溶劑。 When the hole transport layer 2 is formed by the wet film formation method, it is generally the same as the case where the hole injection layer 1 is formed by the wet film formation method, but the composition for forming the hole injection layer is used instead. The composition for forming a hole transport layer can be formed. When the hole transport layer 2 is formed by a wet film formation method, the composition for forming a hole transport layer further contains a solvent. The solvent used for the composition for forming a hole transport layer can be the same solvent as the solvent used for the composition for forming a hole injection layer.

電洞輸送層形成用組成物中的電洞輸送性化合物濃度，係可設定為與電洞注入層形成用組成物中的電洞輸送性化合物濃度為同樣範圍。電洞輸送層利用濕式成膜法的形成係可依照與前述電 洞注入層成膜法同樣地實施。 The concentration of the hole transporting compound in the composition for forming a hole transport layer can be set to be in the same range as the concentration of the hole transporting compound in the composition for forming a hole injection layer. The formation of the hole transport layer by the wet film formation method can be in accordance with the aforementioned electricity The hole injection layer film formation method was carried out in the same manner.

<利用真空蒸鍍法進行電洞輸送層形成> <Formation of hole transport layer by vacuum evaporation method>

相關利用真空蒸鍍法形成電洞輸送層2的情況，通常係與利用真空蒸鍍法形成上述電洞注入層1的情況同樣，只是取代電洞注入層形成用組成物，改為使用電洞輸送層形成用組成物便可形成。蒸鍍時的真空度、蒸鍍速度及溫度等成膜條件等等，係可依照與上述電洞注入層的真空蒸鍍時為同樣條件施行成膜。 In the case where the hole transport layer 2 is formed by a vacuum deposition method, the hole injection layer 1 is formed by a vacuum deposition method, and the hole injection layer formation composition is replaced by a hole. The composition for forming a transport layer can be formed. The film formation conditions such as the degree of vacuum at the time of vapor deposition, the vapor deposition rate, and the temperature can be formed in the same manner as in the vacuum deposition of the above-described hole injection layer.

(發光層) (lighting layer)

發光層3係對一對電極間賦予電場時，藉由從陽極所注入的電洞與從陰極所注入的電子再結合而被激發，屬於負責發光機能的層。發光層3係在陽極6與陰極5之間形成的層，發光層3係當在陽極6上設有電洞注入層1時，便形成於電洞注入層1與陰極5之間，當在陽極6上設有電洞輸送層2時，便形成於電洞輸送層2與陰極5之間。 When the light-emitting layer 3 applies an electric field between a pair of electrodes, it is excited by recombination of a hole injected from the anode and electrons injected from the cathode, and belongs to a layer responsible for the light-emitting function. The light-emitting layer 3 is a layer formed between the anode 6 and the cathode 5, and when the hole injection layer 1 is provided on the anode 6, it is formed between the hole injection layer 1 and the cathode 5, when When the hole transport layer 2 is provided on the anode 6, it is formed between the hole transport layer 2 and the cathode 5.

發光層3的膜厚係在不致明顯損及本發明效果之前提下，可為任意，但就從膜不易生成缺陷的觀點，越厚越佳，又另一方面，就從較容易低驅動電壓的觀點，越薄越佳。所以，較佳係3nm以上、更佳係5nm以上，又另一方面，通常較佳係200nm以下、更佳係100nm以下。發光層3係至少含有具發光性質的材料(發光材料)，且含有具電荷輸送性的材料(電荷輸送性材料)。 The film thickness of the light-emitting layer 3 can be raised without significantly impairing the effects of the present invention, but it is preferable from the viewpoint that the film is less likely to be defective, and on the other hand, it is easier to drive the voltage. The thinner the better. Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is usually preferably 200 nm or less, more preferably 100 nm or less. The light-emitting layer 3 contains at least a material having a light-emitting property (a light-emitting material) and a material having a charge transport property (a charge transporting material).

(發光材料) (Luminescent material)

發光材料係在依所需發光波長發光，不致損及本發明效果之前提下，其餘並無特別的限制，可使用公知的發光材料。發光材料係可為螢光發光材料、亦可為磷光發光材料，較佳係發光效率良好的材料，就從內部量子效率的觀點，較佳係磷光發光材料。 The luminescent material is emitted at a desired illuminating wavelength, and is not particularly limited until the effect of the present invention is impaired, and the rest is not particularly limited, and a known luminescent material can be used. The luminescent material may be a fluorescent luminescent material or a phosphorescent luminescent material, and is preferably a material having good luminescence efficiency, and is preferably a phosphorescent luminescent material from the viewpoint of internal quantum efficiency.

螢光發光材料係可例如以下材料。提供藍色發光的螢光發光材料(藍色螢光發光材料)，係可例如：萘、苝、芘、蒽、香豆素、、對雙(2-苯基乙烯基)苯、及該等的衍生物等。提供綠色發光的螢光發光材料(綠色螢光發光材料)，係可例如：喹吖酮衍生物、香豆素衍生物、Al(C₉H₆NO)₃等鋁錯合物等等。 The fluorescent material can be, for example, the following materials. Providing a blue-emitting fluorescent material (blue fluorescent material), for example, naphthalene, anthracene, anthracene, anthracene, coumarin, , p-bis(2-phenylvinyl)benzene, and the like. A green light-emitting fluorescent material (green fluorescent material) is provided, which may be, for example, a quinophthalone derivative, a coumarin derivative, an aluminum complex such as Al(C ₉ H ₆ NO) ₃ or the like.

提供黃色發光的螢光發光材料(黃色螢光發光材料)，係可例如紅熒烯、呸啶酮衍生物等。提供紅色發光的螢光發光材料(紅色螢光發光材料)，係可例如：DCM(4-(二氰基亞甲基)-2-甲基-6-(對甲胺基苯乙烯)-4H-吡喃)系化合物、苯并吡喃衍生物、若丹明衍生物、苯并硫衍生物、氮雜苯并硫(azabenzothioxanthene)等。 A yellow-emitting fluorescent material (yellow fluorescent material) is provided, which may be, for example, rubrene, an acridone derivative or the like. Providing a red-emitting fluorescent material (red fluorescent material), for example, DCM (4-(dicyanomethylidene)-2-methyl-6-(p-methylaminostyrene)-4H -pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzo sulfur Derivative, azabenzo sulfur (azabenzothioxanthene) and the like.

再者，磷光發光材料係可例如含有從長週期型週期表(以下在無特別聲明之前提下稱「週期表」的情況，係指長週期型週期表)第7~11族中所選擇金屬的有機金屬錯合物等。從週期表之第7~11族中所選擇的金屬，較佳係可舉例如：釕、銠、鈀、銀、錸、鋨、銥、白金、金等。 Further, the phosphorescent material may, for example, contain metals selected from Groups 7 to 11 of the long-period periodic table (hereinafter referred to as "periodic table" before the special statement, which refers to the long-period periodic table) Organic metal complexes, etc. The metal selected from Groups 7 to 11 of the periodic table may preferably be, for example, ruthenium, rhodium, palladium, silver, rhodium, iridium, iridium, platinum, gold or the like.

有機金屬錯合物的配位基，較佳係(雜)芳基吡啶配位基、(雜)芳基吡唑配位基等(雜)芳基、與吡啶、吡唑、菲咯啉等相連結的配位基，更佳係苯基吡啶配位基、苯基吡唑配位基。此處所謂「(雜) 芳基」係指芳基或雜芳基。 a ligand of the organometallic complex, preferably a (hetero)arylpyridine ligand, a (hetero)arylpyrazole ligand or the like (hetero)aryl group, and a pyridine, pyrazole, phenanthroline, etc. The coordinating ligand is more preferably a phenylpyridine ligand or a phenylpyrazole ligand. Here is called "(heterogeneous) "Aryl" means an aryl or heteroaryl group.

較佳的磷光發光材料，具體係可例如：三(2-苯基吡啶)銥、三(2-苯基吡啶)釕、三(2-苯基吡啶)鈀、雙(2-苯基吡啶)白金、三(2-苯基吡啶)鋨、三(2-苯基吡啶)錸等苯基吡啶錯合物；以及八乙基白金卟啉、八苯基白金卟啉、八乙基鈀卟啉、八苯基鈀卟啉等卟啉錯合物等等。 Preferred phosphorescent materials are, for example, tris(2-phenylpyridine)fluorene, tris(2-phenylpyridine)iridium, tris(2-phenylpyridine)palladium, bis(2-phenylpyridine). a phenylpyridine complex such as platinum, tris(2-phenylpyridine)fluorene or tris(2-phenylpyridine)anthracene; and octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethylpalladium porphyrin a porphyrin complex such as octaphenyl palladium porphyrin or the like.

高分子系發光材料係可舉例如：聚(9,9-二辛基茀-2,7-二基)、聚[(9,9-二辛基茀-2,7-二基)-co-(4,4'-(N-(4-第二丁基苯基))二苯基胺)]、聚[(9,9-二辛基茀-2,7-二基)-co-(1,4-苯并-2{2,1'-3}-***)]等聚茀系材料；聚[2-甲氧基-5-(2-戊基己氧基)-1,4-苯亞乙烯]等聚苯亞乙烯系材料。 The polymer light-emitting material may, for example, be poly(9,9-dioctylfluorene-2,7-diyl) or poly[(9,9-dioctylfluorene-2,7-diyl)-co. -(4,4'-(N-(4-t-butylphenyl))diphenylamine)], poly[(9,9-dioctylfluoren-2,7-diyl)-co- (1,4-benzo-2)2,1'-3}-triazole)] is a polyfluorene-based material; poly[2-methoxy-5-(2-pentylhexyloxy)-1, Polyphenylene vinylene material such as 4-phenylene vinylene].

(電荷輸送性材料) (charge transport material)

電荷輸送性材料係具有正電荷(電洞)或負電荷(電子)輸送性的材料，在不致損及本發明效果之前提下，其餘並無特別的限制，可使用公知的發光材料。電荷輸送性材料係可使用習知在有機電場發光元件的發光層中所使用的化合物等，特別較佳係當作發光層主材料使用的化合物。 The charge transporting material is a material having positive charge (hole) or negative charge (electron) transportability, and is not particularly limited until it is detrimental to the effects of the present invention, and a known luminescent material can be used. As the charge transporting material, a compound or the like which is conventionally used in the light-emitting layer of the organic electroluminescent element can be used, and a compound which is used as a main material of the light-emitting layer is particularly preferable.

電荷輸送性材料具體係可例如：芳香族胺系化合物、酞菁系化合物、卟啉系化合物、寡噻吩系化合物、聚噻吩系化合物、苄基苯系化合物、利用茀基連結三級胺的化合物、腙系化合物、矽氮烷系化合物、矽烷胺系化合物、磷胺系化合物、喹吖酮系化合物等當作 電洞注入層之電洞輸送性化合物所例示的化合物等等，此外尚可例如：蒽系化合物、芘系化合物、咔唑系化合物、吡啶系化合物、菲咯啉系化合物、二唑系化合物、矽諾魯系化合物等電子輸送性化合物等等。 The charge transporting material may specifically be, for example, an aromatic amine compound, a phthalocyanine compound, a porphyrin compound, an oligothiophene compound, a polythiophene compound, a benzylbenzene compound, or a compound in which a tertiary amine is bonded by a mercapto group. a compound exemplified as a hole transporting compound which is a hole injecting layer, such as an anthraquinone compound, a decane compound, a decylamine compound, a phosphoramide compound, or a quinophthalone compound, and the like. : an anthraquinone compound, an oxime compound, an oxazole compound, a pyridine compound, a phenanthroline compound, An electron transporting compound such as a bisazole compound or a quinolol compound.

再者，較佳亦可使用例如：4,4'-雙[N-(1-萘基)-N-苯基胺基]聯苯所代表，由含有2個以上三級胺的2個以上縮合芳香族環，取代氮原子的芳香族二胺(日本專利特開平5-234681號公報)；4,4',4"-三(1-萘基苯基胺基)三苯胺等具有星爆式結構的芳香族胺系化合物(J.Lumin.，第72-74卷、第985頁、1997年)；由三苯胺的四聚體所構成芳香族胺系化合物(Chem.Commun.，第2175頁、1996年)；2,2',7,7'-四(二苯基胺基)-9,9'-螺雙茀等茀系化合物(Synth.Metals，第91卷、第209頁、1997年)；4,4'-N,N'-二咔唑聯苯等咔唑系化合物等等，當作電洞輸送層之電洞輸送性化合物所例示的化合物等。又，其他尚可例如：2-(4-伸聯苯基)-5-(對第三丁基苯基)-1,3,4-二唑(tBU-PBD)、2,5-雙(1-萘基)-1,3,4-二唑(BND)等二唑系化合物；2,5-雙(6'-(2',2"-聯二吡啶))-1,1-二甲基-3,4-二苯基矽諾魯(PyPySPyPy)等矽諾魯系化合物、向二氮雜菲(BPhen)、2,9-二甲基-4,7-二苯基-1,10-菲咯啉[bathocuproine(BCP，浴銅靈)]等菲咯啉系化合物等等。 Further, it is preferably represented by, for example, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl, which is composed of two or more containing two or more tertiary amines. Aromatic diamine which condenses an aromatic ring and a nitrogen atom (Japanese Patent Laid-Open No. Hei 5-234681); starburst with 4,4',4"-tris(1-naphthylphenylamino)triphenylamine Aromatic amine-based compounds of the formula (J. Lumin., vol. 72-74, p. 985, 1997); aromatic amine compounds composed of tetramers of triphenylamine (Chem. Commun., 2175) Page, 1996); 2,2',7,7'-tetrakis(diphenylamino)-9,9'-spirobifluorene and other lanthanide compounds (Synth.Metals, Vol. 91, p. 209, 1997); an oxazole compound such as 4,4'-N, N'-dicarbazole biphenyl, etc., as a compound exemplified as a hole transporting compound in a hole transport layer. For example: 2-(4-Exbiphenyl)-5-(p-tert-butylphenyl)-1,3,4- Diazole (tBU-PBD), 2,5-bis(1-naphthyl)-1,3,4- Diazole (BND), etc. Diazole compound; 2,5-bis(6'-(2',2"-bibipyridine))-1,1-dimethyl-3,4-diphenylnonol (PyPySPyPy) Noro compounds, phenanthroline (BPhen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline [bathocuproine (BCP, bath copper)] A porphyrin compound or the like.

<利用濕式成膜法施行發光層形成> <Formation of luminescent layer by wet film formation method>

發光層3之形成方法係可為真空蒸鍍法、亦可為濕式成膜法，就從成膜性優異的觀點，較佳係濕式成膜法、更佳係旋塗法及噴墨法。 當利用濕式成膜法形成發光層時，通常係與上述利用濕式成膜法形成電洞注入層的情況同樣，只是取代電洞注入層形成用組成物，改為使用經與能溶解成為發光層之材料的溶劑(發光層用溶劑)相混合，而製備的發光層形成用組成物便可形成。 The method of forming the light-emitting layer 3 may be a vacuum deposition method or a wet film formation method, and is preferably a wet film formation method, a better spin coating method, and an ink jet method from the viewpoint of excellent film formability. law. When the light-emitting layer is formed by the wet film formation method, it is usually the same as the case where the hole injection layer is formed by the wet film formation method, and the composition for forming the hole injection layer is replaced by the use of The solvent (the solvent for the light-emitting layer) of the material of the light-emitting layer is mixed, and the prepared composition for forming a light-emitting layer can be formed.

溶劑係可例如針對電洞注入層之形成所舉例的醚系溶劑、酯系溶劑、芳香族烴系溶劑、醯胺系溶劑，其他尚可例如：烷烴系溶劑、鹵化芳香族烴系溶劑、脂肪族醇系溶劑、脂環族醇系溶劑、脂肪族酮系溶劑及脂環族酮系溶劑等。以下舉的溶劑具體例，在不致損及本發明效果之前提下，不僅侷限於該等。 The solvent may be, for example, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent or a guanamine solvent, which is exemplified for the formation of the hole injection layer, and may be, for example, an alkane solvent, a halogenated aromatic hydrocarbon solvent, or a fat. The alcohol-based solvent, the alicyclic alcohol-based solvent, the aliphatic ketone solvent, and the alicyclic ketone solvent. Specific examples of the solvent to be exemplified below are not limited to these, unless they are detrimental to the effects of the present invention.

例如：乙二醇二甲醚、乙二醇二***、丙二醇-1-單甲醚醋酸酯(PGMEA)等脂肪族醚系溶劑；1,2-二甲氧基苯、1,3-二甲氧基苯、茴香醚、苯***、2-甲氧基甲苯、3-甲氧基甲苯、4-甲氧基甲苯、2,3-二甲基茴香醚、2,4-二甲基茴香醚、二苯醚等芳香族醚系溶劑；醋酸苯酯、丙酸苯酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸正丁酯等芳香族酯系溶劑；甲苯、二甲苯、亞磷酸三甲酯、環己苯、四磷、3-異丙基聯苯、1,2,3,4-四甲基苯、1,4-二異丙基苯、環己苯、甲基萘等芳香族烴系溶劑；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺系溶劑；正癸烷、環己烷、乙基環己烷、十氫化萘、雙環己烷等烷烴系溶劑；氯化苯、二氯化苯、三氯化苯等鹵化芳香族烴系溶劑；丁醇、己醇等脂肪族醇系溶劑；環己醇、環辛醇等脂環族醇系溶劑；甲乙酮、二丁酮等脂肪族酮系溶劑；環己酮、環辛酮、葑酮(fenchone)等脂環族酮系溶劑等等。該等之中，較佳係烷烴系溶劑及芳 香族烴系溶劑。 For example: an aliphatic ether solvent such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethyl Oxybenzene, anisole, phenylethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole An aromatic ether solvent such as diphenyl ether; an aromatic ester such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, ethyl benzoate, propyl benzoate or n-butyl benzoate; Solvent; toluene, xylene, trimethyl phosphite, cyclohexylbenzene, tetraphosphorus, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene An aromatic hydrocarbon solvent such as cyclohexylbenzene or methylnaphthalene; a guanamine solvent such as N,N-dimethylformamide or N,N-dimethylacetamide; n-decane, cyclohexane, An alkane solvent such as ethylcyclohexane, decalin or bicyclohexane; a halogenated aromatic hydrocarbon solvent such as chlorinated benzene, dichlorobenzene or trichlorobenzene; or an aliphatic alcohol solvent such as butanol or hexanol. ; cycloaliphatic alcohol solvent such as cyclohexanol or cyclooctanol; fat such as methyl ethyl ketone or dibutyl ketone Aliphatic ketone solvent; cyclohexanone, cyclooctanone, fenchone (fenchone) alicyclic ketone solvents and the like. Among these, alkane-based solvents and aromatics are preferred. An aromatic hydrocarbon solvent.

(電洞阻止層) (hole blocking layer)

亦可在發光層3與後述電子注入層4之間設置電洞阻止層(未圖示)。電洞阻止層係在發光層3上，依鄰接發光層3靠陰極5側之界面的方式積層之層。 A hole blocking layer (not shown) may be provided between the light-emitting layer 3 and the electron injection layer 4 to be described later. The hole blocking layer is layered on the light-emitting layer 3 so as to be adjacent to the interface of the light-emitting layer 3 on the cathode 5 side.

該電洞阻止層係具有：阻止從陽極6移動至的電洞到達陰極5之功用、以及將從陰極5所注入的電子效率佳地朝發光層3方向輸送的功用。對構成電洞阻止層的材料所要求物性，係可例如：電子移動率高、電洞移動率低、能隙(HOMO、LUMO之差)大、激發三重態能階(T1)高。 The hole prevention layer has a function of preventing a hole moved from the anode 6 from reaching the cathode 5, and a function of efficiently transporting electrons injected from the cathode 5 toward the light-emitting layer 3. The physical properties required for the material constituting the hole blocking layer can be, for example, high electron mobility, low hole mobility, large energy gap (difference between HOMO and LUMO), and high excitation triplet energy level (T1).

滿足此種條件的電洞阻止層之材料，係可例如：雙(2-甲基-8-羥基喹啉)(酚鹽)鋁、雙(2-甲基-8-羥基喹啉)(三苯基矽烷鹽)鋁等混合配位基錯合物；雙(2-甲基-8-羥基喹啉)鋁-μ-氧基-雙-(2-甲基-8-羥基喹啉)鋁雙核金屬錯合物等金屬錯合物；二苯乙烯基聯苯衍生物等苯乙烯化合物(日本專利特開平11-242996號公報)；3-(4-聯苯基)-4-苯基-5(4-第三丁基苯基)-1,2,4-***等***衍生物(日本專利特開平7-41759號公報)；浴銅靈(bathocuproine)等菲咯啉衍生物(日本專利特開平10-79297號公報)等等。又，國際公開第2005/022962號所記載至少具有1個2,4,6位被取代之吡啶環的化合物，亦屬於較佳的電洞阻止層材料。 The material of the hole stop layer satisfying such conditions may be, for example, bis(2-methyl-8-hydroxyquinoline) (phenate) aluminum, bis(2-methyl-8-hydroxyquinoline) (three) Phenyl decane salt) mixed complex complex such as aluminum; bis(2-methyl-8-hydroxyquinoline) aluminum-μ-oxy-bis-(2-methyl-8-hydroxyquinoline) aluminum a metal complex such as a dinuclear metal complex; a styrene compound such as a distyrylbiphenyl derivative (Japanese Patent Laid-Open No. Hei 11-242996); 3-(4-biphenyl)-4-phenyl- a triazole derivative such as 5 (4-tert-butylphenyl)-1,2,4-triazole (Japanese Patent Laid-Open No. Hei 7-41759); a phenanthroline derivative such as bathocuproine ( Japanese Patent Laid-Open No. Hei 10-79297, and the like. Further, a compound having at least one substituted pyridine ring of 2, 4, and 6 as described in International Publication No. 2005/022962 is also a preferred material for the hole blocking layer.

電洞阻止層之形成方法並無限制。所以，可利用濕式成 膜法、蒸鍍法、或其他方法形成。電洞阻止層的膜厚係在不致明顯損及本發明效果之前提下可為任意，通常係0.3nm以上、較佳係0.5nm以上，又通常係100nm以下、較佳係50nm以下。 The method of forming the hole blocking layer is not limited. Therefore, wet type can be utilized Formed by a film method, an evaporation method, or other methods. The film thickness of the hole blocking layer may be any thickness before the effect of the present invention is not significantly impaired, and is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.

(電子輸送層) (electron transport layer)

電子輸送層係在為更加提升元件電流效率之目的下，設置於發光層3與電子注入層4之間(未圖示)。電子輸送層係在賦予電場的電極間，由能將從陰極所注入的電子效率佳地朝發光層3方向輸送之化合物形成。電子輸送層所使用的電子輸送性化合物，必需屬於從陰極或電子注入層的電子注入效率高、且具有高電子移動率、能將所注入電子效率佳地輸送之化合物。 The electron transport layer is provided between the light-emitting layer 3 and the electron injection layer 4 for the purpose of further improving the current efficiency of the element (not shown). The electron transport layer is formed of a compound capable of efficiently transporting electrons injected from the cathode toward the light-emitting layer 3 between the electrodes to which the electric field is applied. The electron transporting compound used in the electron transporting layer is required to have a high electron injecting efficiency from the cathode or the electron injecting layer, and has a high electron mobility and can efficiently transport the injected electrons efficiently.

電子輸送層所使用的電子輸送性化合物，通常較佳係從陰極或電子注入層的電子注入效率高、能將所注入電子效率佳地輸送之化合物。電子輸送性化合物具體係可例如：8-羥基喹啉的鋁錯合物等金屬錯合物(日本專利特開昭59-194393號公報)；10-羥苯并[h]喹啉的金屬錯合物、二唑衍生物、二苯乙烯基聯苯衍生物、矽諾魯衍生物、3-羥基黃酮金屬錯合物、5-羥基黃酮金屬錯合物、苯并唑金屬錯合物、苯并噻唑金屬錯合物、三苯并咪唑苯(米國特許第5645948號說明書)、喹啉化合物(日本專利特開平6-207169號公報)、菲咯啉衍生物(日本專利特開平5-331459號公報)、2-第三丁基-9,10-N,N'-二氰基蒽醌二亞胺、n型氫化非晶質碳化矽、n型硫化鋅、n型硒化鋅等。 The electron transporting compound used in the electron transporting layer is usually preferably a compound having high electron injection efficiency from the cathode or the electron injecting layer and capable of efficiently transporting the injected electrons. The electron transporting compound may specifically be, for example, a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open Publication No. SHO 59-194393); a metal complex of 10-hydroxybenzo[h]quinoline Compound, Diazole derivatives, distyrylbiphenyl derivatives, indole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzo Oxazole metal complex, benzothiazole metal complex, tribenzimidazole benzene (Mr. Patent No. 5645948), quin A porphyrin compound (Japanese Patent Laid-Open No. Hei 6-207169), a phenanthroline derivative (Japanese Patent Laid-Open No. Hei 5-331459), 2-tert-butyl-9,10-N,N'-dicyano group Diimine, n-type hydrogenated amorphous tantalum carbide, n-type zinc sulfide, n-type zinc selenide, and the like.

電子輸送層的膜厚通常係1nm以上、較佳係5nm以上， 又另一方面，通常係300nm以下、較佳係100nm以下。電子輸送層係與上述同樣的，藉由利用濕式成膜法、或真空蒸鍍法積層於電洞阻止層上而形成。通常係採取真空蒸鍍法。 The film thickness of the electron transport layer is usually 1 nm or more, preferably 5 nm or more. On the other hand, it is usually 300 nm or less, preferably 100 nm or less. The electron transport layer is formed by laminating on the hole blocking layer by a wet film formation method or a vacuum deposition method in the same manner as described above. Vacuum evaporation is usually employed.

(電子注入層) (electron injection layer)

電子注入層4係具有將從陰極5所注入的電子，效率佳地注入於電子輸送層或發光層3的功用。為能效率佳執行電子注入，形成電子注入層4的材料較佳係功函數低的金屬。可使用例如鈉、銫等鹼金屬；鋇、鈣等鹼土族金屬等等。其膜厚通常較佳係0.1nm以上、且5nm以下。 The electron injection layer 4 has a function of efficiently injecting electrons injected from the cathode 5 into the electron transport layer or the light-emitting layer 3. In order to perform electron injection with high efficiency, the material forming the electron injecting layer 4 is preferably a metal having a low work function. An alkali metal such as sodium or cesium; an alkaline earth metal such as barium or calcium, or the like can be used. The film thickness is usually preferably 0.1 nm or more and 5 nm or less.

又，在向二氮雜菲等含氮雜環化合物、或8-羥基喹啉的鋁錯合物等金屬錯合物所代表之有機電子輸送材料中，摻雜入鈉、鉀、銫、鋰、銣等鹼金屬(日本專利特開平10-270171號公報、日本專利特開2002-100478號公報、日本專利特開2002-100482號公報等所記載)，亦能兼顧電子注入‧輸送性提升、及優異膜質，故屬較佳。 Further, an organic electron transporting material represented by a metal complex such as a nitrogen-containing heterocyclic compound such as phenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with sodium, potassium, rubidium or lithium. In addition, it is also possible to achieve both electron injection and transportability improvement, as described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. 2002-100478, and Japanese Patent Application Laid-Open No. Hei No. 2002-100482. And excellent film quality, so it is better.

電子注入層4的膜厚通常係5nm以上、較佳係10nm以上，又通常係200nm以下、較佳係100nm以下的範圍。電子注入層4係藉由依照濕式成膜法或真空蒸鍍法，積層於發光層或其上面的電洞阻止層上而形成。濕式成膜法時的詳細內容係與前述發光層的情況同樣。 The thickness of the electron injecting layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less. The electron injection layer 4 is formed by laminating on the light-emitting layer or the hole blocking layer on the light-emitting layer or the vacuum deposition method. The details of the wet film formation method are the same as those of the above-mentioned light-emitting layer.

(陰極) (cathode)

陰極5係具有朝靠發光層3側的層(電子注入層或發光層等)中注入 電子的功用。陰極5的材料係可使用上述陽極6所使用的材料，在效率佳執行電子注入的前提下，較佳係使用低功函數金屬，可使用例如：錫、鎂、銦、鈣、鋁、銀等金屬、或該等的合金等。具體例係可例如：鎂-銀合金、鎂-銦合金、鋁-鋰合金等低功函數合金電極等等。 The cathode 5 has an injection into a layer (electron injection layer, light-emitting layer, etc.) on the side of the light-emitting layer 3 The function of electronics. The material of the cathode 5 can use the material used for the anode 6 described above. Under the premise of performing electron injection with high efficiency, it is preferable to use a low work function metal, and for example, tin, magnesium, indium, calcium, aluminum, silver, etc. can be used. Metal, or such alloys, and the like. Specific examples may be, for example, a low work function alloy electrode such as a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-lithium alloy.

就從元件安定性的觀點，較佳係在陰極5上積層著功函數高、對大氣呈安定的金屬層，俾保護由低功函數金屬構成的陰極。所積層的金屬係可例如：鋁、銀、銅、鎳、鉻、金、白金等金屬。陰極的膜厚通常係與陽極同樣。 From the viewpoint of component stability, it is preferable to laminate a metal layer having a high work function and a stable atmosphere on the cathode 5, and to protect a cathode composed of a low work function metal. The metal layer to be laminated may be, for example, a metal such as aluminum, silver, copper, nickel, chromium, gold or platinum. The film thickness of the cathode is usually the same as that of the anode.

(其他的層) (other layers)

本發明的有機電場發光元件100係在不致損及本發明效果之前提下，尚可更進一步設有其他的層。即在陽極6與陰極5之間，亦可設有上述之外的其他任意層。 The organic electroluminescent device 100 of the present invention can be further provided with other layers without impairing the effects of the present invention. That is, between the anode 6 and the cathode 5, any other layer than the above may be provided.

<其他的元件構成> <Other components>

另外，亦可與上述所說明呈顛倒的構造，即在基板8上依序積層著陰極5、電子注入層4、發光層3、電洞注入層1、陽極6。 Alternatively, the cathode 5, the electron injection layer 4, the light-emitting layer 3, the hole injection layer 1, and the anode 6 may be laminated on the substrate 8 in a reversed configuration as described above.

<其他> <Other>

將本發明的有機電場發光元件100使用於有機電場發光裝置時，可使用為單一的有機電場發光元件，亦可由複數有機電場發光元件呈陣列狀配置構成使用，構成陽極與陰極呈X-Y矩陣狀配置使用。 When the organic electroluminescence device 100 of the present invention is used in an organic electric field light-emitting device, a single organic electric field light-emitting device may be used, or a plurality of organic electro-optic light-emitting devices may be arranged in an array, and the anode and the cathode may be arranged in an XY matrix. use.

VI.有機EL顯示裝置 VI. Organic EL display device

本發明的有機EL顯示裝置係使用上述本發明的有機電場發光元 件。相關本發明有機EL顯示裝置的型式與構造並無特別的限制，可使用本發明的有機電場發光元件依照常法進行組裝。例如依照「有機EL顯示器」(歐姆公司、平成16年8月20日出版、時任靜士、安達千波矢、村田英幸著)所記載的方法，便可形成本發明的有機EL顯示裝置。 The organic EL display device of the present invention uses the above-described organic electric field light-emitting element of the present invention. Pieces. The type and structure of the organic EL display device of the present invention are not particularly limited, and the organic electroluminescent device of the present invention can be assembled in accordance with a conventional method. For example, the organic EL display device of the present invention can be formed by the method described in "Organic EL Display" (Oh, Inc., published on August 20, 2006, at the time of Shimishi, Anda Chiba, and Murata Yuki).

VII.有機EL照明 VII. Organic EL lighting

本發明的有機EL照明係使用上述本發明的有機電場發光元件。相關本發明有機EL照明的型式與構造並無特別的限制，可使用本發明的有機電場發光元件依照常法進行組裝。 The organic EL illumination of the present invention uses the above-described organic electroluminescent device of the present invention. The type and structure of the organic EL illumination of the present invention are not particularly limited, and the organic electroluminescence device of the present invention can be assembled in accordance with a conventional method.

實施例 Example

以下，藉由製造例、實施例及比較例，針對本發明進行更進一步具體說明，惟本發明在不逾越主旨之前提下，並不僅侷限於以下的實施例。 Hereinafter, the present invention will be further specifically described by way of the production examples, the examples, and the comparative examples, but the present invention is not limited to the following examples, and is not limited to the following examples.

1. Haze、全光線穿透率之測定 1. Haze, determination of total light transmittance

當作散射膜用的散射層、及光取出膜的Haze值、全光線穿透率，係使用SUGA試驗機(股)製霧度電腦HZ-2型，並以D65光源為光源進行測定。霧度電腦的0、100值組合係在未放入樣品狀態(即僅有空氣的狀態)實施。所以，後述散射層及光取出膜的Haze值與全光線穿透率，係包括玻璃基板(日本電氣硝子(股)製玻璃基板「OA-10G」(厚0.7mm))的Haze特性、全光線穿透率特性之值。另外，僅單獨測定該玻璃基板時的Haze係0.00、全光線穿透率係91.8%。 The Haze value and the total light transmittance of the scattering layer for the scattering film and the light extraction film were measured by a haze computer model HZ-2 manufactured by a SUGA tester (manufacturing unit), and the D65 light source was used as a light source. The 0, 100 value combination of the haze computer is implemented in a state where the sample is not placed (that is, in a state where only air is present). Therefore, the Haze value and the total light transmittance of the scattering layer and the light extraction film, which will be described later, include Haze characteristics and total light of a glass substrate (OA-10G (0.7 mm thick) of a glass substrate (Nippon Electric Glass Co., Ltd.). The value of the permeability characteristic. Further, the Haze system 0.00 and the total light transmittance of the glass substrate alone were 91.8%.

2.膜厚、表面粗糙度Ra之測定 2. Determination of film thickness and surface roughness Ra

散射層與光取出膜的膜厚係使用KLA-Tencor Japan公司製的梯度‧表面粗糙度‧細微形狀測定裝置(「P-15型」)進行測定。表面粗糙度係測定2000μm間的算術平均粗糙度Ra。 The film thickness of the scattering layer and the light extraction film was measured using a gradient ‧ surface roughness ‧ fine shape measuring device ("P-15 type") manufactured by KLA-Tencor Japan Co., Ltd. The surface roughness was measured as the arithmetic mean roughness Ra between 2000 μm.

3.利用掃描式電子顯微鏡(SEM)進行的表面觀察及EDX分析 3. Surface observation and EDX analysis using scanning electron microscopy (SEM)

樣品片經施行Au-Pd蒸鍍後，使用日立製掃描式電子顯微鏡S-4100型，依加速電壓15kV測定SEM影像。EDX(能量散佈式X射線分光法)分析係利用Bruker公司Quantax200(檢測器：XFlash4010)進行測定。 After the sample piece was subjected to Au-Pd vapor deposition, the SEM image was measured at an acceleration voltage of 15 kV using a Hitachi scanning electron microscope model S-4100. The EDX (energy dispersive X-ray spectroscopy) analysis was performed using a Bruker Quantax 200 (detector: XFlash 4010).

4.金屬氧化物分散液之平均粒徑測定 4. Determination of average particle size of metal oxide dispersion

金屬氧化物分散液的平均粒徑係使用大塚電子股份有限公司製的濃厚系粒徑分析儀(FPAR-1000型、動態光散射法)進行測定。一次粒徑係利用製造者的公布值。 The average particle diameter of the metal oxide dispersion liquid was measured using a thick particle size analyzer (FPAR-1000 type, dynamic light scattering method) manufactured by Otsuka Electronics Co., Ltd. The primary particle size utilizes the published value of the manufacturer.

5.聚矽烷之分子量 5. Molecular weight of polydecane

利用所使用聚矽烷化合物所附的製造者試驗成績表之值。 The value of the manufacturer's test score table attached to the polydecane compound used is utilized.

大阪瓦斯化學(股)製聚矽烷「OGSOL® SI-20-10(改)」的分子量(Mw及Mn)係1200、900。同「OGSOL® SI-20-10」的分子量(Mw及Mn)係1500、800。同「OGSOL® SI-10-10」的分子量(Mw及Mn)係13800、1900。同「OGSOL® SI-10-20」的分子量(Mw及Mn)係1600、1100。又，因為同「OGSOL® SI-30-10」係十苯基環戊烯矽烷(CAS編號 1770-54-3)，因而分子量係911。 The molecular weight (Mw and Mn) of the polyoxane "OGSOL® SI-20-10 (modified)" manufactured by Osaka Gas Chemical Co., Ltd. is 1200 and 900. The molecular weight (Mw and Mn) of "OGSOL® SI-20-10" is 1500 or 800. The molecular weight (Mw and Mn) of "OGSOL® SI-10-10" is 13800 and 1900. The molecular weight (Mw and Mn) of "OGSOL® SI-10-20" is 1600 and 1100. Also, because it is the same as "OGSOL® SI-30-10", decaphenylcyclopentene decane (CAS number) 1770-54-3), thus having a molecular weight of 911.

6.聚矽烷化合物之取代基莫耳比率(甲基、苯基比率)測定 6. Determination of substituent molar ratio (methyl, phenyl ratio) of polydecane compounds

將聚矽烷溶解於重氯仿中，利用Bruker公司NMR(400MHz)測定質子NMR並定量。大阪瓦斯化學(股)製聚矽烷「OGSOL® SI-20-10(改)」的取代基莫耳比率(甲基：苯基)係約1：3。同「OGSOL® SI-20-10」的取代基莫耳比率(甲基：苯基)係約1：10。同「OGSOL® SI-10-10」的取代基莫耳比率(甲基：苯基)係約1：1。同「OGSOL® SI-10-20」的取代基莫耳比率(甲基：苯基)係約1：2。 The polydecane was dissolved in heavy chloroform, and proton NMR was measured and quantified by Bruker NMR (400 MHz). The substitution molar ratio (methyl:phenyl) of polyoxane "OGSOL® SI-20-10 (modified)" manufactured by Osaka Gas Chemical Co., Ltd. is about 1:3. The substitution molar ratio (methyl:phenyl) to "OGSOL® SI-20-10" is about 1:10. The substitution molar ratio (methyl:phenyl) of "OGSOL® SI-10-10" is about 1:1. The substitution molar ratio (methyl:phenyl) to "OGSOL® SI-10-20" is about 1:2.

7.金屬氧化物分散液中的分散劑成分、及市售分散劑的結構鑑定 7. Structure identification of dispersant components in metal oxide dispersions and commercially available dispersants

將金屬氧化物分散液的溶劑予以蒸發除去，利用重氯仿/重DMSO溶劑進行再溶解，使用Bruker公司NMR(400MHz)測定質子NMR，鑑定一次結構。BYK Japan公司製氧化鋅奈米粒子分散液「NANOBYK-3841」的分散劑成分結構，確認到含有六亞甲基二胺基甲酸酯、丁氧基聚丙二醇、聚己內酯。御國色素(股)製氧化鈦粒子分散液「No.280」的分散劑成分結構，確認到含有碳數15~20之羥基不飽和脂肪酸的聚酯(n=10以下)、與N,N-二甲基丙二胺的醯胺化物，以及更進一步四級銨鹽化物。BYK Japan公司製分散劑「DISPERBYK-111」的結構，確認到含有聚乙二醇、聚己內酯、磷酸酯。BYK Japan公司製分散劑「BYK-9077」的結構，確認到含有六亞甲基二胺基甲酸酯、丁氧基聚丙二醇、聚己內酯。另外，相關ZRPMAl5WT%-E5、御國色素No.280及NANOBYK-3812，並無法確認到有胺基甲酸酯化合物的 存在。 The solvent of the metal oxide dispersion was removed by evaporation, re-dissolved with a heavy chloroform/heavy DMSO solvent, and proton NMR was measured using Bruker NMR (400 MHz) to identify the primary structure. The dispersant component structure of the zinc oxide nanoparticle dispersion liquid "NANOBYK-3841" manufactured by BYK Japan Co., Ltd. was confirmed to contain hexamethylene dicarbamate, butoxy polypropylene glycol, and polycaprolactone. The dispersant component structure of the titanium oxide particle dispersion "No. 280" manufactured by Yuki Co., Ltd. was confirmed to contain a polyester having a carbon number of 15 to 20 hydroxy unsaturated fatty acids (n = 10 or less) and N, N. - a amide of dimethyl propylene diamine, and further a quaternary ammonium salt. The structure of the dispersant "DISPERBYK-111" manufactured by BYK Japan Co., Ltd. was confirmed to contain polyethylene glycol, polycaprolactone, and phosphate ester. The structure of the dispersing agent "BYK-9077" manufactured by BYK Japan Co., Ltd. was confirmed to contain hexamethylene dicarbamate, butoxy polypropylene glycol, and polycaprolactone. In addition, related to ZRPMAl5WT%-E5, Yuguo pigment No. 280 and NANOBYK-3812, no urethane compound was confirmed. presence.

(實施例1) (Example 1) <散射層1之形成> <Formation of scattering layer 1>

在大阪瓦斯化學(股)製聚矽烷「OGSOL® SI-20-10(改)」2.0g中添加丙二醇單甲醚醋酸酯(以下稱「PGMEA」)8.0g，使於攪拌下溶解。將該溶液利用0.2μmPTEF過濾器(Autovial AV125EORG)過濾，而製備「SI-20-10(改)PGMEA溶液(20wt%)」。 8.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was added to 2.0 g of polyoxane "OGSOL® SI-20-10 (modified)" manufactured by Osaka Gas Chemical Co., Ltd., and dissolved under stirring. This solution was filtered through a 0.2 μm PTEF filter (Autovial AV125EORG) to prepare "SI-20-10 (modified) PGMEA solution (20% by weight)".

接著，在「SI-20-10(改)PGMEA溶液(20wt%)」1.0g中，添加BYK Japan公司製氧化鋅奈米粒子分散液「NANOBYK-3841」(氧化鋅的一次粒徑40nm、依動態光散射測定的平均粒徑125nm、溶劑物種：PEGMEA)2.0g，使用筆型攪拌器(pencil mixer)攪拌1分鐘，便製備得散射層塗佈液。將該散射層塗佈液在日本電氣硝子(股)製玻璃基板「OA-10G」(37.5mm×25mm×厚0.7mm)上放置0.3ml，施行旋塗塗佈(旋塗機：MIKASA製1H-360S型，先依旋塗轉數：500rpm施行10秒鐘後，再依1000rpm施行30秒鐘)。將該塗佈基板於加熱板上依120℃施行2分鐘的預乾燥，接著依350℃施行30分鐘的正式乾燥。然後，自然放冷，便在玻璃基板上獲得散射層1。 Next, in the "SI-20-10 (modified) PGMEA solution (20 wt%)" 1.0 g, a zinc oxide nanoparticle dispersion "NANOBYK-3841" manufactured by BYK Japan Co., Ltd. was added (the primary particle diameter of zinc oxide was 40 nm, The scattering layer coating liquid was prepared by a dynamic light scattering measurement of an average particle diameter of 125 nm and a solvent species: PEGMEA (2.0 g) and stirring for 1 minute using a pen mixer. The scattering layer coating liquid was placed on a glass substrate "OA-10G" (37.5 mm × 25 mm × thickness 0.7 mm) made of Nippon Electric Glass Co., Ltd., and 0.3 ml was placed thereon, and spin coating was applied (rotary coating machine: 1H manufactured by MIKASA) -360S type, first spin-coating number: 500 rpm for 10 seconds, then 1000 rpm for 30 seconds). The coated substrate was predried on a hot plate at 120 ° C for 2 minutes, and then subjected to formal drying at 350 ° C for 30 minutes. Then, naturally, it is allowed to cool, and the scattering layer 1 is obtained on the glass substrate.

該散射層1經利用掃描式電子顯微鏡(以下稱「SEM」)進行觀察，結果從表面像與截面像均確認到有空隙形成(參照圖1、圖2)。經從圖1所示表面影像求取空隙的平均直徑(平均10個的算術平均值)，結果為330nm。又，同樣的從表面影像求取空隙佔總面積的面積 率，結果為20.4%。 When the scattering layer 1 was observed by a scanning electron microscope (hereinafter referred to as "SEM"), it was confirmed that voids were formed from both the surface image and the cross-sectional image (see FIGS. 1 and 2). The average diameter of the voids (average arithmetic mean of 10) was obtained from the surface image shown in Fig. 1, and the result was 330 nm. Also, the same area from the surface image is taken to calculate the area of the gap. The rate was 20.4%.

再者，該散射層1的膜厚係0.85μm、Haze值係80.8、全光線穿透率係71.9%。又，經稜鏡耦合法測量該塗膜的折射率，結果為2.357(633nm)。 Further, the scattering layer 1 had a film thickness of 0.85 μm, a Haze value of 80.8, and a total light transmittance of 71.9%. Further, the refractive index of the coating film was measured by a ruthenium coupling method and found to be 2.357 (633 nm).

(實施例2~4) (Examples 2 to 4) <散射層2~4之形成> <Formation of scattering layers 2 to 4>

使用依實施例1所製備的散射層塗佈液，依照與實施例1同樣的條件在玻璃基板上施行旋塗塗佈，於加熱板上依120℃施行2分鐘的預乾燥。接著，依220℃(實施例2)、170℃(實施例3)、或120℃(實施例4)施行30分鐘的正式乾燥，經自然放冷，便在玻璃基板上獲得散射層2~4。利用SEM觀察，確認到任一散射層均在表面及截面上有空隙形成。 Using the scattering layer coating liquid prepared in Example 1, spin coating was applied to the glass substrate under the same conditions as in Example 1, and pre-drying was performed on a hot plate at 120 ° C for 2 minutes. Then, it was subjected to formal drying for 30 minutes at 220 ° C (Example 2), 170 ° C (Example 3), or 120 ° C (Example 4), and natural cooling was performed to obtain scattering layers 2 to 4 on the glass substrate. . It was confirmed by SEM observation that any of the scattering layers had voids formed on the surface and the cross section.

(實施例5~11) (Examples 5 to 11) <散射層5~11之形成> <Formation of scattering layers 5 to 11>

除將「SI-20-10(改)PGMEA溶液(20wt%)」及「NANOBYK-3841」的混合重量，變更為下述表1所記載之外，其餘均依照實施例1所記載方法獲得散射層5~8。再者，使用由各產品的聚矽烷溶解於溶劑中而製備的「SI-10-10PGMEA溶液(20wt%)」、「SI-10-20PGMEA溶液(20wt%)」、「SI-30-10四氫呋喃(以下稱「THF」)溶液(10Wt%)」，依表1所記載的混合比製備散射層塗佈液，並依照實施例1所記載方法分別獲得散射層9~11。利用SEM觀察，確認到任一散射層均在表面及截面 上有空隙形成。 The scattering weight of "SI-20-10 (modified) PGMEA solution (20 wt%)" and "NANOBYK-3841" was changed to the following Table 1, and the scattering was obtained according to the method described in Example 1. Layer 5~8. Further, "SI-10-10PGMEA solution (20 wt%)", "SI-10-20PGMEA solution (20 wt%)", "SI-30-10 tetrahydrofuran" prepared by dissolving polydecane in each product in a solvent was used. (hereinafter referred to as "THF") solution (10 wt%), a scattering layer coating liquid was prepared according to the mixing ratio described in Table 1, and scattering layers 9 to 11 were obtained in accordance with the method described in Example 1. Using SEM observation, it was confirmed that any scattering layer was on the surface and cross section. There is a gap formed on it.

(實施例12~15) (Examples 12 to 15) <散射層12~15之形成> <Formation of scattering layers 12 to 15>

使用BYK Japan公司製氧化鋅奈米粒子分散液「NANOBYK-3821」(氧化鋅的一次粒徑20nm、依照動態光散射測定的平均粒徑係98nm、溶劑物種：PEGMEA)、同公司製氧化鋁奈米粒子分散液「NANOBYK-3610」(氧化鋁的一次粒徑20~25nm、依照動態光散射測定的平均粒徑係110nm、溶劑物種：PEGMEA)、及同公司製氧化矽奈米粒子分散液「NANOBYK-3650」(氧化矽的一次粒徑20~25nm、依照動態光散射測定的平均粒徑係未測定、溶劑物種：PEGMEA及甲氧基丙醇)，依照表1所記載的混合比製備散射層塗佈液，利用實施例1所記載的方法分別獲得散射層12~15。利用SEM觀察，確認到任一散射層均在表面及截面上有空隙形成。 A zinc oxide nanoparticle dispersion liquid "NANOBYK-3821" manufactured by BYK Japan Co., Ltd. (primary particle diameter of zinc oxide: 20 nm, average particle diameter measured by dynamic light scattering: 98 nm, solvent species: PEGMEA) was used. Rice particle dispersion "NANOBYK-3610" (primary particle size of alumina is 20 to 25 nm, average particle diameter measured by dynamic light scattering is 110 nm, solvent species: PEGMEA), and dispersion of cerium oxide nanoparticles by the company" NANOBYK-3650" (primary particle size of cerium oxide 20 to 25 nm, average particle diameter measured by dynamic light scattering is not measured, solvent species: PEGMEA and methoxypropanol), and scattering is prepared according to the mixing ratio described in Table 1. In the layer coating liquid, scattering layers 12 to 15 were respectively obtained by the method described in Example 1. It was confirmed by SEM observation that any of the scattering layers had voids formed on the surface and the cross section.

(比較例1) (Comparative Example 1) <散射層16之形成> <Formation of Scattering Layer 16>

除取代實施例1所製備的散射層塗佈液，改為僅使用「NANOBYK-3841」之外，其餘均依照與實施例1同樣的方法，在玻璃基板上獲得散射層16。利用SEM進行表面觀察，確認在散射層16中沒有形成空隙(參照圖3)。 The scattering layer 16 was obtained on the glass substrate in the same manner as in Example 1 except that the scattering layer coating liquid prepared in Example 1 was used instead of "NANOBYK-3841". Surface observation by SEM confirmed that no void was formed in the scattering layer 16 (see Fig. 3).

(比較例2) (Comparative Example 2) <散射層17之形成> <Formation of Scattering Layer 17>

除取代實施例1所製備的散射層塗佈液，僅使用「SI-20-10(改)PGMEA溶液(20wt%)」之外，其均依照與實施例1同樣的方法，在玻璃基板上獲得散射層17。利用SEM進行表面觀察，確認在散射層17中沒有形成空隙(參照圖4)。 The glass substrate was placed on the glass substrate in the same manner as in Example 1 except that the scattering layer coating liquid prepared in Example 1 was used instead of the "SI-20-10 (modified) PGMEA solution (20% by weight)". A scattering layer 17 is obtained. Surface observation by SEM confirmed that no void was formed in the scattering layer 17 (see Fig. 4).

(比較例3~5) (Comparative examples 3 to 5) <散射層18~20之形成> <Formation of scattering layers 18 to 20>

使用CIK奈米科技公司製氧化鋯奈米粒子分散液「ZRPMAl5WT%-E5」(氧化鋯的一次粒徑20nm、依照動態光散射測定的平均粒徑係58nm、溶劑物種：PEGMEA)、御國色素(股)製氧化鈦粒子分散液「No.280」(氧化鈦的依照動態光散射測定的平均粒徑係110nm、溶劑物種：甲苯)、BYK Japan公司製氧化鈰奈米粒子分散液「NANOBYK-3812」(氧化鈰的一次粒徑10nm、依照動態光散射測定的平均粒徑係未測定、溶劑物種：無芳香族白油溶劑)，依照表1所記載的混合比製備散射層塗佈液，依照實施例1所記載方法分別獲得散射層18~20。利用SEM進行表面觀察，確認在散射層18~20中沒有形成空隙。 Zirconium nanoparticles dispersion "ZRPMAl5WT%-E5" manufactured by CIK Nanotech Co., Ltd. (primary particle diameter of zirconia 20 nm, average particle diameter measured by dynamic light scattering: 58 nm, solvent species: PEGMEA), royal pigment (Stock) titanium oxide particle dispersion "No. 280" (average particle diameter of titanium oxide measured by dynamic light scattering: 110 nm, solvent species: toluene), and BYK Japan company's cerium oxide nanoparticle dispersion "NANOBYK- 3812" (the primary particle diameter of cerium oxide is 10 nm, the average particle diameter measured by dynamic light scattering is not measured, solvent species: no aromatic white oil solvent), and the scattering layer coating liquid is prepared according to the mixing ratio described in Table 1, The scattering layers 18 to 20 were respectively obtained in accordance with the method described in Example 1. Surface observation by SEM confirmed that no voids were formed in the scattering layers 18 to 20.

針對散射層1~20測定空隙有無形成、空隙的平均直徑、空隙的面積率、膜厚、Haze值、全光線穿透率、表面粗糙度(Ra)，結果如表2所示。 The presence or absence of void formation, the average diameter of the voids, the area ratio of the voids, the film thickness, the Haze value, the total light transmittance, and the surface roughness (Ra) were measured for the scattering layers 1 to 20. The results are shown in Table 2.

(實施例16) (Embodiment 16) <分散液A之製備> <Preparation of Dispersion A>

在30ml之具蓋的玻璃瓶中，於石原產業(股)製氧化鈦粉末「TTO-51(A)」(1次粒徑10~30nm)1.20g中，加入PEGMEA(4.74g)、BYK Japan製分散劑「BYK-9077」0.24g、及0.5mm二氧化鋯球珠20g，經封栓再利用淺田鐵工製塗料攪拌器(PC型)施行4小時振盪而施行分散處理。該分散液利用200篩目鐵質網施行過濾、去除二氧化鋯球珠，便獲得分散液A。該分散液的平均粒徑係200nm。 In a glass bottle of 30 ml, a 1.20 g of titanium oxide powder "TTO-51 (A)" (primary particle size 10 to 30 nm) made of Ishihara Sangyo Co., Ltd. was added to PEGMEA (4.74 g), BYK Japan. Dispersing agent "BYK-9077" 0.24g, and 0.5mm 20 g of zirconium dioxide beads were subjected to dispersion treatment by blocking and then using a shallow field iron paint spreader (PC type) for 4 hours of shaking. The dispersion was filtered using a 200 mesh iron mesh to remove zirconia beads to obtain a dispersion A. The average particle diameter of the dispersion was 200 nm.

<散射層21之形成> <Formation of Scattering Layer 21>

接著，在「SI-20-10(改)PGMEA溶液(20wt%)」1.0g中添加分散液A(3.6g)，使用筆型攪拌器施行1分鐘攪拌，而製備散射層塗佈液。使用該散射層塗佈液依照實施例1所記載方法形成散射層22。 Then, Dispersion A (3.6 g) was added to 1.0 g of "SI-20-10 (modified) PGMEA solution (20 wt%)", and the mixture was stirred for 1 minute using a pen type stirrer to prepare a scattering layer coating liquid. The scattering layer 22 was formed in accordance with the method described in Example 1 using the scattering layer coating liquid.

(實施例17~20、比較例6) (Examples 17 to 20, Comparative Example 6) <分散液B~F之製備> <Preparation of Dispersion B~F>

除金屬氧化物粉末、分散劑變更為如表3所示之外，其餘均依照實施例16所記載方法製備分散液B~F。 The dispersions B to F were prepared in accordance with the method described in Example 16 except that the metal oxide powder and the dispersant were changed as shown in Table 3.

<散射層22~26之形成> <Formation of scattering layers 22 to 26>

依照表4所記載混合比製備散射層塗佈液，分別依照實施例1所記載方法形成散射層22~26。 The scattering layer coating liquid was prepared in accordance with the mixing ratio described in Table 4, and the scattering layers 22 to 26 were formed in accordance with the method described in Example 1.

針對散射層21~26，測定空隙有無形成、空隙的平均直徑、空隙的面積率，結果如表4所示。由含有屬於胺基甲酸酯化合物之「BYK-9077」分散劑的散射層塗佈液所形成散射層，均有發現空隙形成，而由未含有胺基甲酸酯化合物的散射層塗佈液所形成散射層則沒有發現空隙形成。 The presence or absence of void formation, the average diameter of the voids, and the area ratio of the voids were measured for the scattering layers 21 to 26, and the results are shown in Table 4. A scattering layer formed by a scattering layer coating liquid containing a "BYK-9077" dispersing agent belonging to a urethane compound, and voids were formed, and a scattering layer coating liquid containing no urethane compound was observed. No void formation was observed in the formed scattering layer.

(實施例21~24、比較例7) (Examples 21 to 24, Comparative Example 7) <散射層27~31之形成> <Formation of scattering layers 27 to 31>

在散射層沒有發現空隙形成的比較例2~6之散射層塗佈液中，依表5所示混合比追加添加胺基甲酸酯化合物的「BYK-9077」，而製備新的散射層塗佈液，使用其依照實施例1所記載方法形成散射層27~31。針對散射層27~31，測定空隙有無形成、空隙的平均直徑、空隙的面積率，結果如表5所示。 In the scattering layer coating liquid of Comparative Examples 2 to 6 in which no void formation was observed in the scattering layer, "BYK-9077" in which the urethane compound was additionally added in the mixing ratio shown in Table 5 was prepared to prepare a new scattering layer coating. The cloth liquid was used to form the scattering layers 27 to 31 in accordance with the method described in Example 1. The presence or absence of void formation, the average diameter of the voids, and the area ratio of the voids were measured for the scattering layers 27 to 31. The results are shown in Table 5.

由表5的結果確認到即便後續才追加添加屬於胺基甲酸酯化合物的「BYK-9077」分散劑，仍可獲得在散射層有形成空隙的效果(實施例21~24)。另一方面，在僅使用SI-20-10(改)PGMEA溶液(20wt%)的比較例2之散射層塗佈液中，即便添加屬於胺基甲酸酯化合物的「BYK-9077」分散劑，但在散射層中仍沒有空隙形成(比較例7)。 From the results of Table 5, it was confirmed that even if the "BYK-9077" dispersant belonging to the urethane compound was added in the subsequent manner, the effect of forming voids in the scattering layer was obtained (Examples 21 to 24). On the other hand, in the scattering layer coating liquid of Comparative Example 2 using only the SI-20-10 (modified) PGMEA solution (20% by weight), even the "BYK-9077" dispersing agent belonging to the urethane compound was added. However, no void formation was observed in the scattering layer (Comparative Example 7).

(實施例25) (Embodiment 25) <有機電場發光元件之製作> <Production of Organic Electric Field Light-Emitting Element>

依照以下的方法製作有機電場發光元件。另外，有機電場發光元件的構造係如圖5所示。 An organic electroluminescent element was produced in accordance with the following method. In addition, the structure of the organic electroluminescent element is as shown in FIG.

1.光取出膜A之形成 1. Formation of light extraction film A

在實施例1所製作玻璃基板8上面的散射層1上，放置CIK奈米科技公司製金紅石型氧化鈦奈米粒子分散液「15%RTiO₂0.02um高分散液」(氧化鈦的平均粒徑20nm、固形份濃度15%、溶劑：正丁醇/二丙酮醇=80/20重量比)0.5ml，施行旋塗塗佈(旋塗機：MIKASA製1H-360S型，先依旋塗轉數：500rpm施行10秒鐘後，再依1000rpm施行30秒鐘)。該塗佈基板在加熱板上依120℃施行2分鐘的預乾燥，接著依350℃施行30分鐘正式乾燥。然後，經自然放冷，便獲得在散射層1上積層著氧化鈦奈米粒子層的散射膜7之「光取出膜A」。 On the scattering layer 1 on the glass substrate 8 prepared in Example 1, a rutile-type titanium oxide nanoparticle dispersion liquid "15% RTiO ₂ 0.02 um high dispersion liquid" (manufactured by CIK Nanotech Co., Ltd.) was placed on the scattering layer 1 (average particle of titanium oxide) 20nm diameter, solid concentration 15%, solvent: n-butanol / diacetone alcohol = 80 / 20 weight ratio) 0.5ml, apply spin coating (spin coater: MIKASA 1H-360S type, first spin coating Number: 500 rpm is applied for 10 seconds, and then performed at 1000 rpm for 30 seconds). The coated substrate was predried at 120 ° C for 2 minutes on a hot plate, and then oven dried at 350 ° C for 30 minutes. Then, by natural cooling, the "light extraction film A" of the scattering film 7 in which the titanium oxide nanoparticle layer is laminated on the scattering layer 1 is obtained.

2.陽極之形成 2. Formation of the anode

在上述光取出膜A之上，形成陽極6之由膜厚70nm的銦錫氧化物(ITO)所構成透明導電膜。 On the light extraction film A, a transparent conductive film made of indium tin oxide (ITO) having a thickness of 70 nm of the anode 6 was formed.

3.基板之洗淨 3. Washing the substrate

將上述已形成陽極的玻璃基板，在浸漬於橫濱油脂工業(股)製Semi Clean L.G.L的3%界面活性劑水溶液狀態下，利用超音波洗淨機操作10分鐘後，利用純水進行清洗，再風乾。然後，將經風乾的基板利用UV臭氧洗淨機施行1分鐘的UV臭氧洗淨。 The glass substrate on which the anode was formed was immersed in a 3% surfactant aqueous solution of Semi Clean LGL manufactured by Yokohama Oils and Fats Co., Ltd., and was operated by an ultrasonic cleaner for 10 minutes, and then washed with pure water. Air dried. Then, the air-dried substrate was subjected to UV ozone washing for 1 minute using a UV ozone cleaner.

4.開口堤之形成 4. Formation of the open bank

將昭和電工製SPCM-144(10.0g)、新中村化學製NK Oligo U-6LPA(6.1g)、汽巴日本製IRGACURE 907(0.8g)、及丙二醇單甲醚醋酸酯22.1g進行混合，而製備負型感光性樹脂用液。 SPCM-144 (10.0 g) manufactured by Showa Denko, NK Oligo U-6LPA (6.1 g) manufactured by Shin-Nakamura Chemical Co., Ltd., IMGACURE 907 (0.8 g) manufactured by Ciba, and 22.1 g of propylene glycol monomethyl ether acetate were mixed. A liquid for a negative photosensitive resin was prepared.

在上述陽極6上旋塗塗佈負型感光性樹脂溶液，穿越具有6mm×6mm開口面積的遮光遮罩，利用紫外線照射施行曝光。經利用氫氧四甲銨水溶液施行顯影後，於260℃熱風爐內施行1小時的堤煅燒，便形成堤壁面高度1.4μm、開口面積6mm×6mm的開口堤9。 A negative photosensitive resin solution was spin-coated on the anode 6 and passed through a light-shielding mask having an opening area of 6 mm × 6 mm, and exposure was performed by ultraviolet irradiation. After development by an aqueous solution of tetramethylammonium hydroxide, the bank was calcined in a hot air furnace at 260 ° C for 1 hour to form an open bank 9 having a wall surface height of 1.4 μm and an opening area of 6 mm × 6 mm.

5.電洞注入層之形成 5. Formation of hole injection layer

將具有以下所示重複單元的高分子化合物、與4-異丙基-4-甲基二苯基碘鎓四(五氟苯基)硼酸鹽，依重量比為100：20進行混合，並依混合物的濃度成為2.4重量%之方式添加苯甲酸乙酯，經加熱、溶解而製備電洞注入層形成用組成物。 The polymer compound having the repeating unit shown below and 4-isopropyl-4-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate are mixed at a weight ratio of 100:20, and The benzoic acid ethyl ester was added so as to have a concentration of the mixture of 2.4% by weight, and the composition for forming a hole injection layer was prepared by heating and dissolving.

[化3] [Chemical 3]

上式中，n係3~100000的整數。 In the above formula, n is an integer of 3 to 100000.

將該電洞注入層形成用組成物於大氣環境中，於由上述開口堤9所包圍的陽極6上施行旋塗塗佈(先依旋塗轉數：500rpm施行10秒鐘後，再依1500rpm施行30秒鐘)。該塗佈膜於230℃無塵烤箱內施行加熱而形成膜厚35nm的電洞注入層1。 The hole injection layer forming composition was applied to the anode 6 surrounded by the open bank 9 in an atmosphere, and the spin coating was applied to the anode 6 (first spin coating speed: 500 rpm for 10 seconds, and then 1500 rpm). Execute for 30 seconds). This coating film was heated in a 230 ° C clean oven to form a hole injection layer 1 having a film thickness of 35 nm.

6.電洞輸送層之形成 6. Formation of the hole transport layer

在上述電洞注入層1之上，電洞輸送層係由以下所示化合物利用真空蒸鍍法形成膜厚45nm，便形成電洞輸送層2。 On the hole injection layer 1, the hole transport layer was formed into a hole transport layer 2 by a vacuum deposition method to form a film thickness of 45 nm.

另外，從電洞輸送層的蒸鍍以後起至下述<9.密封>結束為止，均設定在氮環境或真空環境內進行處置，俾避免與氧或水分間的接觸。 In addition, from the time of vapor deposition of the hole transport layer to the end of the following <9. Sealing>, it is set to be treated in a nitrogen atmosphere or a vacuum environment to avoid contact with oxygen or moisture.

7.發光層 7. Light-emitting layer

在上述電洞輸送層2上，發光層3係由參(8-羥基喹啉)鋁(Alq₃)利用真空蒸鍍法形成膜厚60nm。 On the hole transport layer 2, the light-emitting layer 3 was formed into a film thickness of 60 nm by vacuum vapor deposition from ginseng (8-hydroxyquinoline) aluminum (Alq ₃ ).

8.電子注入層及陰極之形成 8. Formation of electron injection layer and cathode

在上述發光層3上，將氟化鋰(LiF)依成為膜厚0.5nm的方式利用真空蒸鍍法施行蒸鍍而形成電子注入層4後，再將鋁依成為膜厚80nm的方式利用真空蒸鍍法施行蒸鍍而形成陰極5。 In the light-emitting layer 3, lithium fluoride (LiF) was deposited by vacuum deposition to form an electron injecting layer 4, and then aluminum was used as a film thickness of 80 nm. The vapor deposition method is performed by vapor deposition to form the cathode 5.

9.密封 9. Seal

接著，在氮套手工作箱中，於錐坑玻璃(即經加工呈凹狀的玻璃)11的凹部中央處黏貼著薄片狀脫水材10，並於外周部塗佈光硬化性樹脂12。將該錐坑玻璃11依覆蓋著從光取出膜7積層至陰極5的積層體方式黏貼玻璃基板8，在僅對有塗佈光硬化性樹脂的區域照射紫外光，而使樹脂硬化便密封，獲得有機電場發光元件100(發光面積：0.36cm²)。依照上述方法所製成有機電場發光元件的概略圖，係如圖5所示。 Next, in the nitrogen hand working box, the sheet-shaped dehydrated material 10 is adhered to the center of the concave portion of the taper glass (that is, the glass which is processed into a concave shape) 11, and the photocurable resin 12 is applied to the outer peripheral portion. The tapered glass 11 is adhered to the glass substrate 8 so as to cover the laminated body from the light extraction film 7 to the cathode 5, and the ultraviolet light is applied to only the region where the photocurable resin is applied, and the resin is cured and sealed. An organic electric field light-emitting element 100 (light-emitting area: 0.36 cm ² ) was obtained. A schematic view of an organic electroluminescent device produced in accordance with the above method is shown in FIG.

(實施例26) (Example 26)

在前述光取出膜A之上，更進一步放置Matsumoto Fine Chemical(股)製有機鈦寡聚物「ORGATIX TA-22」的正丁醇稀釋液(TA-22/正丁醇=10/90重量比)0.5ml，施行旋塗塗佈(先依旋塗轉數：500rpm施行10秒鐘後，再依2000rpm施行30秒鐘)。將該塗佈基板在加熱板上依120℃施行2分鐘的預乾燥，接著再依350℃施行30分鐘 的正式乾燥。然後，經自然放冷，便獲得已積層著散射層1、氧化鈦奈米粒子層、氧化鈦溶膠凝膠層的「光取出膜B」。陽極、基板的洗淨、開口堤、電洞注入層、電洞輸送層、發光層、電子注入層、陰極、密封的形成，係依照實施例25所記載方法獲得有機電場發光元件。 On the above-mentioned light extraction film A, a n-butanol dilution (TA-22/n-butanol = 10/90 by weight ratio) of an organic titanium oligomer "ORGATIX TA-22" manufactured by Matsumoto Fine Chemical Co., Ltd. was further placed. 0.5 ml, spin coating (first spin-coating number: 500 rpm for 10 seconds, then 2000 rpm for 30 seconds). The coated substrate was pre-dried on a hot plate at 120 ° C for 2 minutes, and then applied at 350 ° C for 30 minutes. Formally dry. Then, by naturally cooling, a "light extraction film B" having a scattering layer 1, a titanium oxide nanoparticle layer, and a titanium oxide sol gel layer laminated thereon is obtained. An organic electroluminescent device was obtained in accordance with the method described in Example 25, in which the anode, the substrate were cleaned, the open bank, the hole injection layer, the hole transport layer, the light-emitting layer, the electron injection layer, the cathode, and the seal were formed.

(比較例8) (Comparative Example 8)

除使用玻璃基板(日本電氣硝子(股)製玻璃基板「OA-10G」)，且未形成光取出膜之外，其餘均依照實施例25所記載的方法獲得有機電場發光元件。 An organic electroluminescent device was obtained in accordance with the method described in Example 25, except that a glass substrate ("OA-10G" made of Nippon Electric Glass Co., Ltd.) was used, and a light extraction film was not formed.

依照以下所示方法，針對實施例25、26、及比較例8的有機電場發光元件，評價光取出膜的膜厚、Haze、全光線穿透率、表面粗糙度Ra、ITO蝕刻劑耐性(耐酸性)、基板洗淨耐性、光阻堤製作適合性。又，針對各有機電場發光元件，依照以下所示方法測定發光光的全光束量，並評價光取出倍率。結果如表6所示。 The film thickness, Haze, total light transmittance, surface roughness Ra, and ITO etchant resistance (acid resistance) of the light extraction film were evaluated for the organic electroluminescent elements of Examples 25, 26, and Comparative Example 8 according to the methods described below. Properties), substrate cleaning resistance, and light barrier formation suitability. Moreover, the total beam amount of the luminescent light was measured for each of the organic electroluminescent elements, and the light extraction magnification was evaluated. The results are shown in Table 6.

‧膜厚、Haze、全光線穿透率、表面粗糙度Ra之測定 ‧ Determination of film thickness, Haze, total light transmittance, and surface roughness Ra

前述有機電場發光元件的製作中，於形成陽極之前，使用已形成光取出膜的玻璃基板測定膜厚、Haze、全光線穿透率、及表面粗糙度Ra。 In the production of the organic electroluminescent device, before the formation of the anode, the film thickness, Haze, total light transmittance, and surface roughness Ra were measured using a glass substrate on which the light extraction film was formed.

‧ITO蝕刻劑耐性(耐酸性)之評價 ‧ Evaluation of ITO etchant resistance (acid resistance)

在前述有機電場發光元件之製作中，於形成陽極之前，將已形成光取出膜的玻璃基板，在關東化學(股)製「ITO-02」中依25℃浸漬20分鐘後，經水洗，再目視觀察光取出膜表面的劣化狀況，並依以下基 準「A」~「C」施行評價。 In the production of the organic electroluminescent device, the glass substrate on which the light extraction film has been formed is immersed in "ITO-02" manufactured by Kanto Chemical Co., Ltd. at 25 ° C for 20 minutes, and then washed with water, and then washed. Visually observing the deterioration of the surface of the light extraction film, and based on the following basis Appropriate "A" ~ "C" for evaluation.

A：表面保持試驗前的光澤感。 A: The surface maintained the gloss before the test.

B：表面的光澤感縮有降低、但膜卻有殘留。 B: The gloss of the surface is reduced, but the film remains.

C：膜剝離。 C: Film peeling.

‧基板洗淨耐性之評價 ‧ Evaluation of substrate washability

在前述有機電場發光元件之製作中，依目視觀察已完成<基板之洗淨>的玻璃基板表面劣化狀況，並依以下的基準「A」~「C」進行評價。 In the production of the organic electroluminescent device, the deterioration of the surface of the glass substrate on which the <substrate cleaning> was completed was visually observed, and evaluated according to the following criteria "A" to "C".

A：表面保持試驗前的光澤感。 A: The surface maintained the gloss before the test.

B：表面的光澤感縮有降低、但膜卻有殘留。 B: The gloss of the surface is reduced, but the film remains.

C：膜剝離。 C: Film peeling.

‧光阻堤製作適合性之評價 ‧ Evaluation of suitability of light barriers

在前述有機電場發光元件的製作中，利用光學顯微鏡(倍率5倍)觀察已完成開口堤形成的玻璃基板，並依以下的基準「A」~「C」進行評價。 In the production of the organic electroluminescent device, the glass substrate on which the open bank was formed was observed with an optical microscope (magnification: 5 times), and evaluated according to the following criteria "A" to "C".

A：屬於陽極的ITO層全域完全沒有出現缺損、損傷。 A: There is no defect or damage in the entire ITO layer belonging to the anode.

B：屬於陽極的ITO層端部有出現剝落。 B: Peeling occurred at the end of the ITO layer belonging to the anode.

C：屬於陽極的ITO層剝落係全域均有觀察到。 C: The entire ITO layer spalling system belonging to the anode was observed.

‧發光光的全光束量評價 ‧Full beam quantity evaluation of illuminating light

對所獲得有機電場發光元件施加4.0mA直流電流而使發光時，利 用Labsphere公司製積分球型全光束測定系統測定此時的全光束量[流明(lm)](積分球：SLMS-1011型、二極體陣列分光光度儀：DAS-1100型)。 When a 4.0 mA DC current is applied to the obtained organic electric field light-emitting element to cause light emission, The total beam amount at this time [lumen (lm)] was measured by an integrating sphere type full beam measuring system manufactured by Labsphere (integral sphere: SLMS-1011 type, diode array spectrophotometer: DAS-1100 type).

‧光取出倍率的評價 ‧ Evaluation of light extraction rate

將各有機電場發光元件的全光束量，除以使用未設光取出膜之基板的有機電場發光元件(比較例8)全光束量之值，設定為「光取出倍率」，並計算出。如表6所示，將該發明的散射層使用為光取出膜的有機電場發光元件，相較於沒有使用的情況下，可獲得最大1.51倍的全光束量，確認到光取出效率的提升。 The total beam amount of each of the organic electroluminescent elements was divided by the value of the total beam amount of the organic electroluminescent device (Comparative Example 8) using the substrate on which the light extraction film was not provided, and was set to "light extraction magnification" and calculated. As shown in Table 6, the scattering layer of the present invention was used as an organic electroluminescence device of a light extraction film, and a total beam amount of 1.51 times at maximum was obtained as compared with the case where it was not used, and the improvement in light extraction efficiency was confirmed.

(實施例27) (Example 27) 1.基板之準備 1. Preparation of the substrate

準備在日本電氣硝子(股)製玻璃基板「OA-10G」(37.5mm×25mm×厚0.7mm)上，形成當作陽極用的膜厚70nm之ITO，依發光區域為2mm四方的方式，對ITO施行圖案化加工的基板(以下將此稱「2mm四方元件用ITO基板」)。在該基板已形成ITO膜之一面的對向側之面(光射出面)上，依照實施例1所記載方法形成散射層1。其次，施行「3.基板之洗淨」所記載的洗淨步驟。再者，於ITO面上，依照實施例10所記載的方法施行電洞注入層、電洞輸送層、發光層、電子注入層、陰極、密封的形成，獲得在靠光射出面側有形成散射層1的2mm四方之有機電場發光元件(發光面積：0.04cm²)。 It is prepared to form ITO which is 70 nm thick for the anode on a glass substrate "OA-10G" (37.5 mm × 25 mm × thickness 0.7 mm) made of Nippon Electric Glass Co., Ltd., and the light-emitting region is 2 mm square. The substrate on which ITO is patterned (hereinafter referred to as "2 mm square substrate ITO substrate"). The scattering layer 1 was formed in accordance with the method described in Example 1 on the surface (light emitting surface) on the opposite side of one surface of the ITO film on which the substrate was formed. Next, the washing step described in "3. Cleaning of the substrate" is performed. Further, on the ITO surface, the hole injection layer, the hole transport layer, the light-emitting layer, the electron injection layer, the cathode, and the seal were formed in accordance with the method described in Example 10, and scattering was formed on the light-emitting surface side. 2 mm square organic electric field light-emitting element of layer 1 (light-emitting area: 0.04 cm ² ).

(實施例28~31、比較例9) (Examples 28 to 31, Comparative Example 9)

除散射層1分別改為表7所記載散射層之外，其餘均依照實施例27的方法，獲得靠光射出面側有形成散射層的有機電場元件(實施例28~31)。又，獲得沒有形成散射層的有機電場發光元件(比較例9)。 Except that the scattering layer 1 was changed to the scattering layer described in Table 7, respectively, an organic electric field element having a scattering layer formed on the light-emitting surface side was obtained in accordance with the method of Example 27 (Examples 28 to 31). Further, an organic electroluminescent device in which no scattering layer was formed was obtained (Comparative Example 9).

對所獲得有機電場發光元件施加4.0mA直流電流而使發光時，測定此時的全光束量。如表7所示，光射出面有形成散射層的有機電 場發光元件，相較於沒有形成元件(比較例9)之下，可獲得最大1.27倍的全光束量。確認到本發明的光散射層即便形成於光射出面側之情況，仍可提升光取出效率。 When a direct current of 4.0 mA was applied to the obtained organic electroluminescent element to emit light, the total amount of light beam at this time was measured. As shown in Table 7, the light exiting surface has an organic layer forming a scattering layer. The field light-emitting element was able to obtain a maximum beam amount of 1.27 times as large as that of the non-formed element (Comparative Example 9). It was confirmed that the light-scattering efficiency of the light-scattering layer of the present invention can be improved even when it is formed on the light-emitting surface side.

(實施例32) (Example 32) <散射膜之可撓性評價> <Flexibility Evaluation of Scattering Film>

在具有可撓性的聚醯亞胺薄膜(50mm×50mm×厚0.7mm)上，旋塗塗佈實施例1所記載的散射層塗佈液。(先依旋塗轉數：500rpm施行10秒鐘後，再依1000rpm施行30秒鐘)。將該塗佈基板於加熱板上依120℃施行2分鐘的預乾燥，接著再依220℃施行30分鐘的正式乾燥。然後，經自然放冷，便獲得已形成散射膜的聚醯亞胺薄膜。將該聚醯亞胺薄膜依散射膜在外側的方式，捲繞於直徑5mm不銹鋼棒上。從經捲繞後的聚醯亞胺薄膜上切取SEM樣品，觀察散射膜的表面影像。在散射膜表面尚有確認到空隙形成，完全沒有發現到有從聚醯亞胺薄膜上剝落、散射膜皸裂、因捲繞處理而造成散射膜缺損。再者，重複施行捲繞處理50次後，經目視確認散射膜表面並沒有發現缺損。由以上的結果得知，本發明的散射膜係具有優異可撓性，亦可適用於具可撓性的可撓性基板材料。本發明的散射膜係針對使用具可撓性之可撓性基板材料的有機電場發光元件，仍可使用為能提升光取出效率的膜。 The scattering layer coating liquid described in Example 1 was spin-coated on a flexible polyimide film (50 mm × 50 mm × thickness 0.7 mm). (Firstly, spin-coating number: 500 rpm for 10 seconds, then 1000 rpm for 30 seconds). The coated substrate was predried on a hot plate at 120 ° C for 2 minutes, and then subjected to formal drying at 220 ° C for 30 minutes. Then, by naturally allowing to cool, a polyimide film having a scattering film formed thereon is obtained. The polyimide film was wound on a stainless steel rod having a diameter of 5 mm so that the scattering film was on the outside. The SEM sample was cut out from the wound polyimine film to observe the surface image of the scattering film. The formation of voids was confirmed on the surface of the scattering film, and no peeling of the polyimide film or the scattering of the scattering film was observed at all, and the scattering film was broken by the winding treatment. Further, after repeating the winding treatment for 50 times, no defects were observed by visually confirming the surface of the scattering film. From the above results, the scattering film of the present invention has excellent flexibility and can be applied to a flexible substrate material having flexibility. The scattering film of the present invention is also applicable to an organic electroluminescent device using a flexible flexible substrate material, and can be used as a film capable of improving light extraction efficiency.

針對本發明詳細地參照特定實施形態進行說明，惟在不脫逸本發明的精神與範疇內，均可追加各種變更與修正，此係熟習此技術者可輕易思及。本申請案係以2012年1月10日所提出申請的日本專利申請案(特 願2012-001989)為基礎，參照其內容並爰引於本案中。 The present invention has been described with reference to the specific embodiments thereof, and various changes and modifications may be added without departing from the spirit and scope of the invention. This application is a Japanese patent application filed on January 10, 2012. Based on 2012-001989), reference is made to its contents and is cited in this case.

Claims (15)

一種塗佈用組成物，係含有聚矽烷化合物、金屬氧化物及溶劑。 A coating composition containing a polydecane compound, a metal oxide, and a solvent. 如申請專利範圍第1項之塗佈用組成物，其中，更進一步含有具胺基甲酸酯(carbamate)結構的化合物。 The coating composition according to the first aspect of the invention, further comprising a compound having a carbamate structure. 如申請專利範圍第2項之塗佈用組成物，其中，上述具有胺基甲酸酯結構的化合物係分散劑。 The coating composition according to the second aspect of the invention, wherein the compound having a urethane structure is a dispersing agent. 如申請專利範圍第1至3項中任一項之塗佈用組成物，其中，上述金屬氧化物係從氧化鋅、氧化鈦、鈦酸鋇、氧化鉭、氧化矽、氧化鋁、氧化鋯、氧化鈰及氧化錫中選擇之至少1種。 The coating composition according to any one of claims 1 to 3, wherein the metal oxide is derived from zinc oxide, titanium oxide, barium titanate, cerium oxide, cerium oxide, aluminum oxide, zirconium oxide, or the like. At least one selected from the group consisting of cerium oxide and tin oxide. 如申請專利範圍第1至4項中任一項之塗佈用組成物，其中，上述金屬氧化物的折射率係2.0以上。 The coating composition according to any one of claims 1 to 4, wherein the metal oxide has a refractive index of 2.0 or more. 如申請專利範圍第1至5項中任一項之塗佈用組成物，其中，上述金屬氧化物的平均粒徑係1000nm以下。 The coating composition according to any one of claims 1 to 5, wherein the metal oxide has an average particle diameter of 1000 nm or less. 如申請專利範圍第1至6項中任一項之塗佈用組成物，其中，上述聚矽烷化合物係一般式(2)所示矽網絡聚合物：(R²Si)_n‧‧‧(2)(式(2)中，R²係相同或不同，表示氫原子、烷基、烯基、芳基烷基、芳基、烷氧基、羥基、酚性羥基或胺基；n係4~10000的整數)。 The coating composition according to any one of claims 1 to 6, wherein the polydecane compound is a fluorene network polymer represented by the general formula (2): (R ² Si) _n ‧ ‧ (2 (In the formula (2), R ² is the same or different and represents a hydrogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, a hydroxyl group, a phenolic hydroxyl group or an amine group; n system 4~ 10000 integer). 一種多孔質膜，係藉由使申請專利範圍第1至7項中任一項之塗佈用組成物硬化而獲得。 A porous film obtained by curing the coating composition according to any one of claims 1 to 7. 一種光散射膜，係藉由使申請專利範圍第1至7項中任一項之塗佈用組成物硬化而獲得。 A light-scattering film obtained by hardening the coating composition according to any one of claims 1 to 7. 一種有機電場發光元件，係含有申請專利範圍第9項之光散射膜。 An organic electric field light-emitting element comprising the light-scattering film of claim 9th. 如申請專利範圍第10項之有機電場發光元件，其中，上述光散射膜係配置於基板與陽極之間。 The organic electroluminescent device of claim 10, wherein the light-scattering film is disposed between the substrate and the anode. 如申請專利範圍第11項之有機電場發光元件，其中，上述基板係具可撓性的可撓性基板。 The organic electroluminescent device of claim 11, wherein the substrate is a flexible flexible substrate. 一種有機EL顯示裝置，係含有申請專利範圍第10至12項中任一項之有機電場發光元件。 An organic EL display device comprising the organic electroluminescence device of any one of claims 10 to 12. 一種有機EL照明，係含有申請專利範圍第10至12項中任一項之有機電場發光元件。 An organic EL illumination device comprising the organic electroluminescence device of any one of claims 10 to 12. 一種多孔質膜之製造方法，係將申請專利範圍第1至7項中任一項之塗佈用組成物塗佈於基板上，並去除溶劑。 A method for producing a porous film, which comprises applying the coating composition according to any one of claims 1 to 7 to a substrate, and removing the solvent.